Compositions comprising fluoroolefins and uses thereof

ABSTRACT

The present invention relates to fluoroolefin compositions. The fluoroolefin compositions of the present invention are useful as refrigerants or heat transfer fluids and in processes for producing cooling or heat. Additionally, the fluoroolefin compositions of the present invention may be used to replace currently used refrigerant or heat transfer fluid compositions that have higher global warming potential.

CROSS REFERENCE(S) TO RELATED APPLICATION(S)

This application is a divisional application of and claims the prioritybenefit of U.S. patent application Ser. No. 14/603,740 filed Jan. 23,2015, now U.S. Pat. No. 9,410,064, which is a divisional of U.S. patentapplication Ser. No. 14/539,341 filed Nov. 12, 2014, now U.S. Pat. No.9,540,557, which is a divisional of U.S. patent application Ser. No.13/850,338 filed Mar. 26, 2013 and issued as U.S. Pat. No. 8,911,640,which is a division of U.S. patent application Ser. No. 13/286,765 filedNov. 1, 2011 and issued as U.S. Pat. No. 8,425,795, which is a divisionof U.S. patent application Ser. No. 12/696,793 filed Jan. 29, 2010 andissued as U.S. Pat. No. 8,070,976, which is a division of U.S. patentapplication Ser. No. 11/589,588, filed Oct. 30, 2006 and issued as U.S.Pat. No. 7,708,903, now abandoned, which claims the priority benefit ofU.S. Provisional Application 60/732,581, filed Nov. 1, 2005.

FIELD OF THE INVENTION

The present invention relates to compositions for use in refrigeration,air-conditioning or heat pump systems wherein the composition comprisesat least one fluoroolefin. The compositions of the present invention areuseful in processes for producing refrigeration or heat, as heattransfer fluids and many other uses.

BACKGROUND OF THE INVENTION

The refrigeration industry has been working for the past few decades tofind replacement refrigerants for the ozone depletingchlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) beingphased out as a result of the Montreal Protocol. The solution for mostrefrigerant producers has been the commercialization ofhydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants, HFC-134abeing the most widely used at this time, have zero ozone depletionpotential and thus are not affected by the current regulatory phase outas a result of the Montreal Protocol.

Further environmental regulations may ultimately cause global phase outof certain HFC refrigerants. Currently, the automobile industry isfacing regulations relating to global warming potential for refrigerantsused in mobile air-conditioning. Therefore, there is a great currentneed to identify new refrigerants with reduced global warming potentialfor the mobile air-conditioning market. Should the regulations be morebroadly applied in the future, an even greater need will be felt forrefrigerants that can be used in all areas of the refrigeration andair-conditioning industry.

Currently proposed replacement refrigerants for HFC-134a includeHFC-152a, pure hydrocarbons such as butane or propane, or “natural”refrigerants such as CO₂. Many of these suggested replacements aretoxic, flammable, and/or have low energy efficiency. Therefore, newalternative refrigerants are being sought.

The object of the present invention is to provide novel refrigerantcompositions and heat transfer fluid compositions that provide uniquecharacteristics to meet the demands of low or zero ozone depletionpotential and lower global warming potential as compared to currentrefrigerants.

BRIEF SUMMARY OF THE INVENTION

The present invention relates to a refrigerant or heat transfer fluidcomposition comprising at least one compound selected from the groupconsisting of:

-   -   (i) fluoroolefins of the formula E- or Z-R¹CH═CHR², wherein R¹        and R² are, independently, C₁ to C₆ perfluoroalkyl groups, and        wherein the total number of carbons in the compound is at least        5;    -   (ii) cyclic fluoroolefins of the formula        cyclo-[CX═CY(CZW)_(n)—], wherein X, Y, Z, and W, independently,        are H or F, and n is an integer from 2 to 5; and    -   (iii) fluoroolefins selected from the group consisting of:        -   2,3,3-trifluoro-1-propene (CHF₂CF═CH₂);            1,1,2-trifluoro-1-propene (CH₃CF═CF₂);            1,2,3-trifluoro-1-propene (CH₂FCF═CF₂);            1,1,3-trifluoro-1-propene (CH₂FCH═CF₂);            1,3,3-trifluoro-1-propene (CHF₂CH═CHF);            1,1,1,2,3,4,4,4-octafluoro-2-butene (CF₃CF═CFCF₃);            1,1,2,3,3,4,4,4-octafluoro-1-butene (CF₃CF₂CF═CF₂);            1,1,1,2,4,4,4-heptafluoro-2-butene (CF₃CF═CHCF₃);            1,2,3,3,4,4,4-heptafluoro-1-butene (CHF═CFCF₂CF₃);            1,1,1,2,3,4,4-heptafluoro-2-butene (CHF₂CF═CFCF₃);            1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene            ((CF₃)₂C═CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene            (CF₂═CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene            (CF₂═CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene            (CF₂═CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene            (CF₃CF₂CF═CH₂); 1,3,3,4,4,4-hexafluoro-1-butene            (CHF═CHCF₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene            (CHF═CFCHFCF₃); 1,2,3,3,4,4-hexafluoro-1-butene            (CHF═CFCF₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene            (CHF₂CF═CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene            (CH₂FCF═CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene            (CHF₂CH═CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene            (CF₃CH═CFCHF₂); 1,1,2,3,3,4-hexafluoro-1-butene            (CF₂═CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene            (CF₂═CFCHFCHF₂);            3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH₂═C(CF₃)₂);            1,1,1,2,4-pentafluoro-2-butene (CH₂FCH═CFCF₃);            1,1,1,3,4-pentafluoro-2-butene (CF₃CH═CFCH₂F);            3,3,4,4,4-pentafluoro-1-butene (CF₃CF₂CH═CH₂);            1,1,1,4,4-pentafluoro-2-butene (CHF₂CH═CHCF₃);            1,1,1,2,3-pentafluoro-2-butene (CH₃CF═CFCF₃);            2,3,3,4,4-pentafluoro-1-butene (CH₂═CFCF₂CHF₂);            1,1,2,4,4-pentafluoro-2-butene (CHF₂CF═CHCHF₂);            1,1,2,3,3-pentafluoro-1-butene (CH₃CF₂CF═CF₂);            1,1,2,3,4-pentafluoro-2-butene (CH₂FCF═CFCHF₂);            1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF₂═C(CF₃)(CH₃));            2-(difluoromethyl)-3,3,3-trifluoro-1-propene            (CH₂═C(CHF₂)(CF₃)); 2,3,4,4,4-pentafluoro-1-butene            (CH₂═CFCHFCF₃); 1,2,4,4,4-pentafluoro-1-butene            (CHF═CFCH₂CF₃); 1,3,4,4,4-pentafluoro-1-butene            (CHF═CHCHFCF₃); 1,3,3,4,4-pentafluoro-1-butene            (CHF═CHCF₂CHF₂); 1,2,3,4,4-pentafluoro-1-butene            (CHF═CFCHFCHF₂); 3,3,4,4-tetrafluoro-1-butene            (CH₂═CHCF₂CHF₂); 1,1-difluoro-2-(difluoromethyl)-1-propene            (CF₂═C(CHF₂)(CH₃)); 1,3,3,3-tetrafluoro-2-methyl-1-propene            (CHF═C(CF₃)(CH₃)); 3,3-difluoro-2-(difluoromethyl)-1-propene            (CH₂═C(CHF₂)₂); 1,1,1,2-tetrafluoro-2-butene (CF₃CF═CHCH₃);            1,1,1,3-tetrafluoro-2-butene (CH₃CF═CHCF₃);            1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF₃CF═CFCF₂CF₃);            1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF₂═CFCF₂CF₂CF₃);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene            ((CF₃)₂C═CHCF₃); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene            (CF₃CF═CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene            (CF₃CH═CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene            (CHF═CFCF₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene            (CF₂═CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene            (CF₂═CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene            (CHF₂CF═CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene            (CF₃CF═CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene            (CF₃CF═CFCHFCF₃);            1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CHF═CFCF(CF₃)₂);            1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CFCH(CF₃) 2);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene            (CF₃CH═C(CF₃)₂);            1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CHCF(CF₃)₂); 2,3,3,4,4,5,5,5-octafluoro-1-pentene            (CH₂═CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene            (CHF═CFCF₂CF₂CHF₂);            3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene            (CH₂═C(CF₃)CF₂CF₃);            1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CHCH(CF₃)₂);            1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene            (CHF═CHCF(CF₃)₂);            1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene            (CF₂═C(CF₃)CH₂CF₃);            3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            ((CF₃)₂CFCH═CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene            (CF₃CF₂CF₂CH═CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene            (CH₂═CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene            (CF₂═CHCF₂CH₂CF₃);            1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene            (CF₃CF═C(CF₃)(CH₃));            2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            (CH₂═CFCH(CF₃)₂);            1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            (CHF═CHCH(CF₃)₂);            1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene            (CH₂FCH═C(CF₃)₂);            1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene            (CH₃CF═C(CF₃)₂);            1,1,1-trifluoro-2-(trifluoromethyl)-2-butene            ((CF₃)₂C═CHCH₃); 3,4,4,5,5,5-hexafluoro-2-pentene            (CF₃CF₂CF═CHCH₃); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene            (CF₃C(CH₃)═CHCF₃); 3,3,4,5,5,5-hexafluoro-1-pentene            (CH₂═CHCF₂CHFCF₃);            4,4,4-trifluoro-3-(trifluoromethyl)-1-butene            (CH₂═C(CF₃)CH₂CF₃);            1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene            (CF₃(CF₂)₃CF═CF₂);            1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene            (CF₃CF₂CF═CFCF₂CF₃);            1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene            ((CF₃)₂C═C(CF₃)₂);            1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene            ((CF₃)₂CFCF═CFCF₃);            1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene            ((CF₃)₂C═CHC₂F₅);            1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene            ((CF₃)₂CFCF═CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene            (CF₃CF₂CF₂CF₂CH═CH₂);            4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene            (CH₂═CHC(CF₃)₃);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene            ((CF₃)₂C═C(CH₃)(CF₃));            2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene            (CH₂═CFCF₂CH(CF₃)₂);            1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene            (CF₃CF═C(CH₃)CF₂CF₃);            1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene            (CF₃CH═CHCH(CF₃)₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene            (CF₃CF₂CF₂CF═CHCH₃); 3,3,4,4,5,5,6,6-octafluoro1-hexene            (CH₂═CHCF₂CF₂CF₂CHF₂);            1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene            ((CF₃)₂C═CHCF₂CH₃);            4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene            (CH₂═C(CF₃)CH₂C₂F₅);            3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene            (CF₃CF₂CF₂C(CH₃)═CH₂); 4,4,5,5,6,6,6-heptafluoro-2-hexene            (CF₃CF₂CF₂CH═CHCH₃); 4,4,5,5,6,6,6-heptafluoro-1-hexene            (CH₂═CHCH₂CF₂C₂F₅); 1,1,1,2,2,3,4-heptafluoro-3-hexene            (CF₃CF₂CF═CFC₂H₅);            4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene            (CH₂═CHCH₂CF(CF₃)₂);            1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene            (CF₃CF═CHCH(CF₃)(CH₃));            1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene            ((CF₃)₂C═CFC₂H₅);            1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene            (CF₃CF═CFCF₂CF₂C₂F₅);            1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene            (CF₃CF₂CF═CFCF₂C₂F₅);            1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene            (CF₃CH═CFCF₂CF₂C₂F₅);            1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene            (CF₃CF═CHCF₂CF₂C₂F₅);            1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene            (CF₃CF₂CH═CFCF₂C₂F₅);            1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene            (CF₃CF₂CF═CHCF₂C₂F₅); CF₂═CFOCF₂CF₃ (PEVE) and CF₂═CFOCF₃            (PMVE).

The present invention further relates to a composition comprising: (i)at least one fluoroolefin compound; and (ii) at least one flammablerefrigerant; wherein said fluoroolefin is selected from the groupconsisting of:

-   -   (a) fluoroolefins of the formula E- or Z-R¹CH═CHR², wherein R¹        and R² are, independently, C₁ to C₆ perfluoroalkyl groups;    -   (b) cyclic fluoroolefins of the formula cyclo-[CX═CY(CZW)_(n)—],        wherein X, Y, Z, and W, independently, are H or F, and n is an        integer from 2 to 5; and    -   (c) fluoroolefins selected from the group consisting of:        -   1,2,3,3,3-pentafluoro-1-propene (CF₃CF═CHF);            1,1,3,3,3-pentafluoro-1-propene (CF₃CH═CF₂);            1,1,2,3,3-pentafluoro-1-propene (CHF₂CF═CF₂);            1,1,1,2,3,4,4,4-octafluoro-2-butene (CF₃CF═CFCF₃);            1,1,2,3,3,4,4,4-octafluoro-1-butene (CF₃CF₂CF═CF₂);            1,1,1,2,4,4,4-heptafluoro-2-butene (CF₃CF═CHCF₃);            1,2,3,3,4,4,4-heptafluoro-1-butene (CHF═CFCF₂CF₃);            1,1,1,2,3,4,4-heptafluoro-2-butene (CHF₂CF═CFCF₃);            1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene            ((CF₃)₂C═CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene            (CF₂═CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene            (CF₂═CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene            (CF₂═CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene            (CF₃CF₂CF═CH₂); 1,3,3,4,4,4-hexafluoro-1-butene            (CHF═CHCF₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene            (CHF═CFCHFCF₃); 1,2,3,3,4,4-hexafluoro-1-butene            (CHF═CFCF₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene            (CHF₂CF═CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene            (CH₂FCF═CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene            (CHF₂CH═CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene            (CF₃CH═CFCHF₂); 1,1,2,3,3,4-hexafluoro-1-butene            (CF₂═CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene            (CF₂═CFCHFCHF₂);            3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH₂═C(CF₃)₂);            1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF₃CF═CFCF₂CF₃);            1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF₂═CFCF₂CF₂CF₃);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene            ((CF₃)₂C═CHCF₃); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene            (CF₃CF═CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene            (CF₃CH═CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene            (CHF═CFCF₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene            (CF₂═CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene            (CF₂═CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene            (CHF₂CF═CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene            (CF₃CF═CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene            (CF₃CF═CFCHFCF₃);            1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CHF═CFCF(CF₃)₂);            1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CFCH(CF₃) 2);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene            (CF₃CH═C(CF₃)₂);            1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CHCF(CF₃)₂); 2,3,3,4,4,5,5,5-octafluoro-1-pentene            (CH₂═CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene            (CHF═CFCF₂CF₂CHF₂);            3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene            (CH₂═C(CF₃)CF₂CF₃);            1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CHCH(CF₃)₂);            1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene            (CHF═CHCF(CF₃)₂);            1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene            (CF₂═C(CF₃)CH₂CF₃);            3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            ((CF₃)₂CFCH═CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene            (CF₃CF₂CF₂CH═CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene            (CH₂═CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene            (CF₂═CHCF₂CH₂CF₃);            1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene            (CF₃CF═C(CF₃)(CH₃));            2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            (CH₂═CFCH(CF₃)₂);            1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            (CHF═CHCH(CF₃)₂);            1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene            (CH₂FCH═C(CF₃)₂);            1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene            (CH₃CF═C(CF₃)₂);            1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene            (CF₃(CF₂)₃CF═CF₂);            1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene            (CF₃CF₂CF═CFCF₂CF₃);            1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene            ((CF₃)₂C═C(CF₃)₂);            1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene            ((CF₃)₂CFCF═CFCF₃);            1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene            ((CF₃)₂C═CHC₂F₅);            1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene            ((CF₃)₂CFCF═CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene            (CF₃CF₂CF₂CF₂CH═CH₂);            4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene            (CH₂═CHC(CF₃)₃);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene            ((CF₃)₂C═C(CH₃)(CF₃));            2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene            (CH₂═CFCF₂CH(CF₃)₂);            1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene            (CF₃CF═C(CH₃)CF₂CF₃);            1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene            (CF₃CH═CHCH(CF₃)₂);            1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene            (CF₃CF═CFCF₂CF₂C₂F₅);            1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene            (CF₃CF₂CF═CFCF₂C₂F₅);            1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene            (CF₃CH═CFCF₂CF₂C₂F₅);            1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene            (CF₃CF═CHCF₂CF₂C₂F₅);            1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene            (CF₃CF₂CH═CFCF₂C₂F₅); and            1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene            (CF₃CF₂CF═CHCF₂C₂F₅).            The present invention further relates to a method of using a            refrigerant or heat transfer fluid composition in            refrigeration, air-conditioning, or heat pump apparatus,            said method comprising introducing said composition into            said apparatus having (a) centrifugal compressor; (b)            multi-stage centrifugal compressor, or (c) single            slab/single pass heat exchanger; wherein said refrigerant or            heat transfer composition is employed in said apparatus to            result in heating or cooling; and wherein said refrigerant            or heat transfer composition comprises at least one            fluoroolefin selected from the group consisting of:    -   (i) fluoroolefins of the formula E- or Z-R¹CH═CHR², wherein R¹        and R² are, independently, C₁ to C₆ perfluoroalkyl groups;    -   (ii) cyclic fluoroolefins of the formula        cyclo-[CX═CY(CZW)_(n)—], wherein X, Y, Z, and W, independently,        are H or F, and n is an integer from 2 to 5; or    -   (iii) fluoroolefins selected from the group consisting of:        -   1,2,3,3,3-pentafluoro-1-propene (CF₃CF═CHF);            1,1,3,3,3-pentafluoro-1-propene (CF₃CH═CF₂);            1,1,2,3,3-pentafluoro-1-propene (CHF₂CF═CF₂);            1,2,3,3-tetrafluoro-1-propene (CHF₂CF═CHF);            2,3,3,3-tetrafluoro-1-propene (CF₃CF═CH₂);            1,3,3,3-tetrafluoro-1-propene (CF₃CH═CHF);            1,1,2,3-tetrafluoro-1-propene (CH₂FCF═CF₂);            1,1,3,3-tetrafluoro-1-propene (CHF₂CH═CF₂);            2,3,3-trifluoro-1-propene (CHF₂CF═CH₂);            3,3,3-trifluoro-1-propene (CF₃CH═CH₂);            1,1,2-trifluoro-1-propene (CH₃CF═CF₂);            1,1,3-trifluoro-1-propene (CH₂FCH═CF₂);            1,2,3-trifluoro-1-propene (CH₂FCF═CHF);            1,3,3-trifluoro-1-propene (CHF₂CH═CHF);            1,1,1,2,3,4,4,4-octafluoro-2-butene(CF₃CF═CFCF₃);            1,1,2,3,3,4,4,4-octafluoro-1-butene (CF₃CF₂CF═CF₂);            1,1,1,2,4,4,4-heptafluoro-2-butene (CF₃CF═CHCF₃);            1,2,3,3,4,4,4-heptafluoro-1-butene (CHF═CFCF₂CF₃);            1,1,1,2,3,4,4-heptafluoro-2-butene (CHF₂CF═CFCF₃);            1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene            ((CF₃)₂C═CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene            (CF₂═CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene            (CF₂═CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene            (CF₂═CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene            (CF₃CF₂CF═CH₂); 1,3,3,4,4,4-hexafluoro-1-butene            (CHF═CHCF₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene            (CHF═CFCHFCF₃); 1,2,3,3,4,4-hexafluoro-1-butene            (CHF═CFCF₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene            (CHF₂CF═CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene            (CH₂FCF═CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene            (CHF₂CH═CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene            (CF₃CH═CFCHF₂); 1,1,2,3,3,4-hexafluoro-1-butene            (CF₂═CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene            (CF₂═CFCHFCHF₂);            3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH₂═C(CF₃)₂);            1,1,1,2,4-pentafluoro-2-butene (CH₂FCH═CFCF₃);            1,1,1,3,4-pentafluoro-2-butene (CF₃CH═CFCH₂F);            3,3,4,4,4-pentafluoro-1-butene (CF₃CF₂CH═CH₂);            1,1,1,4,4-pentafluoro-2-butene (CHF₂CH═CHCF₃);            1,1,1,2,3-pentafluoro-2-butene (CH₃CF═CFCF₃);            2,3,3,4,4-pentafluoro-1-butene (CH₂═CFCF₂CHF₂);            1,1,2,4,4-pentafluoro-2-butene (CHF₂CF═CHCHF₂);            1,1,2,3,3-pentafluoro-1-butene (CH₃CF₂CF═CF₂);            1,1,2,3,4-pentafluoro-2-butene (CH₂FCF═CFCHF₂);            1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF₂═C(CF₃)(CH₃));            2-(difluoromethyl)-3,3,3-trifluoro-1-propene            (CH₂═C(CHF₂)(CF₃)); 2,3,4,4,4-pentafluoro-1-butene            (CH₂═CFCHFCF₃); 1,2,4,4,4-pentafluoro-1-butene            (CHF═CFCH₂CF₃); 1,3,4,4,4-pentafluoro-1-butene            (CHF═CHCHFCF₃); 1,3,3,4,4-pentafluoro-1-butene            (CHF═CHCF₂CHF₂); 1,2,3,4,4-pentafluoro-1-butene            (CHF═CFCHFCHF₂); 3,3,4,4-tetrafluoro-1-butene            (CH₂═CHCF₂CHF₂); 1,1-difluoro-2-(difluoromethyl)-1-propene            (CF₂═C(CHF₂)(CH₃)); 1,3,3,3-tetrafluoro-2-methyl-1-propene            (CHF═C(CF₃)(CH₃)); 2-difluoromethyl-3,3-difluoro-1-propene            (CH₂═C(CHF₂)₂); 1,1,1,2-tetrafluoro-2-butene (CF₃CF═CHCH₃);            1,1,1,3-tetrafluoro-2-butene (CH₃CF═CHCF₃);            1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF₃CF═CFCF₂CF₃);            1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF₂═CFCF₂CF₂CF₃);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene            ((CF₃)₂C═CHCF₃); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene            (CF₃CF═CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene            (CF₃CH═CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene            (CHF═CFCF₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene            (CF₂═CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene            (CF₂═CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene            (CHF₂CF═CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene            (CF₃CF═CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene            (CF₃CF═CFCHFCF₃);            1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CHF═CFCF(CF₃)₂);            1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CFCH(CF₃) 2);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene            (CF₃CH═C(CF₃)₂);            1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CHCF(CF₃)₂); 2,3,3,4,4,5,5,5-octafluoro-1-pentene            (CH₂═CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene            (CHF═CFCF₂CF₂CHF₂);            3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene            (CH₂═C(CF₃)CF₂CF₃);            1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CHCH(CF₃)₂);            1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene            (CHF═CHCF(CF₃)₂);            1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene            (CF₂═C(CF₃)CH₂CF₃);            3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            ((CF₃)₂CFCH═CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene            (CF₃CF₂CF₂CH═CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene            (CH₂═CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene            (CF₂═CHCF₂CH₂CF₃);            1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene            (CF₃CF═C(CF₃)(CH₃));            2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            (CH₂═CFCH(CF₃)₂);            1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            (CHF═CHCH(CF₃)₂);            1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene            (CH₂FCH═C(CF₃)₂);            1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene            (CH₃CF═C(CF₃)₂);            1,1,1-trifluoro-2-(trifluoromethyl)-2-butene            ((CF₃)₂C═CHCH₃); 3,4,4,5,5,5-hexafluoro-2-pentene            (CF₃CF₂CF═CHCH₃); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene            (CF₃C(CH₃)═CHCF₃); 3,3,4,5,5,5-hexafluoro-1-pentene            (CH₂═CHCF₂CHFCF₃);            3-(trifluoromethyl)-4,4,4-trifluoro-1-butene            (CH₂═C(CF₃)CH₂CF₃);            1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene            (CF₃(CF₂)₃CF═CF₂);            1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene            (CF₃CF₂CF═CFCF₂CF₃);            1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene            ((CF₃)₂C═C(CF₃)₂);            1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene            ((CF₃)₂CFCF═CFCF₃);            1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene            ((CF₃)₂C═CHC₂F₅);            1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene            ((CF₃)₂CFCF═CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene            (CF₃CF₂CF₂CF₂CH═CH₂);            4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene            (CH₂═CHC(CF₃)₃);            1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene            ((CF₃)₂C═C(CH₃)(CF₃));            2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene            (CH₂═CFCF₂CH(CF₃)₂);            1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene            (CF₃CF═C(CH₃)CF₂CF₃);            1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene            (CF₃CH═CHCH(CF₃)₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene            (CF₃CF₂CF₂CF═CHCH₃); 3,3,4,4,5,5,6,6-octafluoro-1-hexene            (CH₂═CHCF₂CF₂CF₂CHF₂);            1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene            ((CF₃)₂C═CHCF₂CH₃);            4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene            (CH₂═C(CF₃)CH₂C₂F₅);            3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene            (CF₃CF₂CF₂C(CH₃)═CH₂); 4,4,5,5,6,6,6-heptafluoro-2-hexene            (CF₃CF₂CF₂CH═CHCH₃); 4,4,5,5,6,6,6-heptafluoro-1-hexene            (CH₂═CHCH₂CF₂C₂F₅); 1,1,1,2,2,3,4-heptafluoro-3-hexene            (CF₃CF₂CF═CFC₂H₅);            4,5,5,5-tetrafluoro-4-trifluoromethyl-1-pentene            (CH₂═CHCH₂CF(CF₃)₂);            1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene            (CF₃CF═CHCH(CF₃)(CH₃));            1,1,1,3-tetrafluoro-2-trifluoromethyl-2-pentene            ((CF₃)₂C═CFC₂H₅);            1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene            (CF₃CF═CFCF₂CF₂C₂F₅);            1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene            (CF₃CF₂CF═CFCF₂C₂F₅);            1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene            (CF₃CH═CFCF₂CF₂C₂F₅);            1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene            (CF₃CF═CHCF₂CF₂C₂F₅);            1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene            (CF₃CF₂CH═CFCF₂C₂F₅);            1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene            (CF₃CF₂CF═CHCF₂C₂F₅); CF₂═CFOCF₂CF₃ (PEVE); CF₂═CFOCF₃            (PMVE) and combinations thereof.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to compositions comprising at least onefluoroolefin. By fluoroolefin is meant any compound containing carbon,fluorine and optionally, hydrogen or oxygen that also contains at leastone double bond. These fluoroolefins may be linear, branched or cyclic.

These compositions have a variety of utilities in working fluids, whichinclude use as foaming agents, blowing agents, fire extinguishingagents, heat transfer mediums (such as heat transfer fluids andrefrigerants for use in refrigeration systems, refrigerators,air-conditioning systems, heat pumps, chillers, and the like), to name afew.

A heat transfer fluid (also referred to herein as a heat transfercomposition or heat transfer fluid composition) is a working fluid usedto carry heat from a heat source to a heat sink.

A refrigerant is a compound or mixture of compounds that function as aheat transfer fluid in a cycle wherein the fluid undergoes a phasechange from a liquid to a gas and back.

The present invention provides fluoroolefins having the formula E- orZ-R¹CH═CHR² (Formula I), wherein R¹ and R² are, independently, C₁ to C₆perfluoroalkyl groups. Examples of R′ and R² groups include, but are notlimited to, CF₃, C₂F₅, CF₂CF₂CF₃, CF(CF₃)₂, CF₂CF₂CF₂CF₃, CF(CF₃)CF₂CF₃,CF₂CF(CF₃)₂, C(CF₃)₃, CF₂CF₂CF₂CF₂CF₃, CF₂CF₂CF(CF₃)₂, C(CF₃)₂C₂F₅,CF₂CF₂CF₂CF₂CF₂CF₃, CF(CF₃) CF₂CF₂C₂F₅, and C(CF₃)₂CF₂C₂F₅. In oneembodiment the fluoroolefins of Formula I, have at least about 3 carbonatoms in the molecule. In another embodiment, the fluoroolefins ofFormula I have at least about 4 carbon atoms in the molecule. In yetanother embodiment, the fluoroolefins of Formula I have at least about 5carbon atoms in the molecule. Exemplary, non-limiting Formula Icompounds are presented in Table 1.

TABLE 1 Code Structure Chemical Name F11E CF₃CH═CHCF₃1,1,1,4,4,4-hexafluoro-2-butene F12E CF₃CH═CHC₂F₅1,1,1,4,4,5,5,5-octafluoro-2-pentene F13E CF₃CH═CHCF₂C₂F₅1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene F13iE CF₃CH═CHCF(CF₃)₂1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2-pentene F22EC₂F₅CH═CHC₂F₅ 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene F14ECF₃CH═CH(CF₂)₃CF₃ 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluoro-2-heptene F14iECF₃CH═CHCF₂CF(CF₃)₂ 1,1,1,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)-2-hexene F14sE CF₃CH═CHCF(CF₃)C₂F₅1,1,1,4,5,5,6,6,6-nonfluoro-4-(trifluoromethyl)-2-hexene F14tECF₃CH═CHC(CF₃)₃ 1,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)-2-pentene F23E C₂F₅CH═CHCF₂C₂F₅1,1,1,2,2,5,5,6,6,7,7,7-dodecafluoro-3-heptene F23iE C₂F₅CH═CHCF(CF₃)₂1,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)-3- hexene F15ECF₃CH═CH(CF₂)₄CF₃ 1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluoro-2-octeneF15iE CF₃CH═CH—CF₂CF₂CF(CF₃)₂1,1,1,4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)-2- heptene F15tECF₃CH═CH—C(CF₃)₂C₂F₅1,1,1,5,5,6,6,6-octafluoro-4,4-bis(trifluoromethyl)-2- hexene F24EC₂F₅CH═CH(CF₂)₃CF₃ 1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluoro-3-octeneF24iE C₂F₅CH═CHCF₂CF(CF₃)₂1,1,1,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)-3- heptene F24sEC₂F₅CH═CHCF(CF₃)C₂F₅1,1,1,2,2,5,6,6,7,7,7-undecafluoro-5-(trifluoromethyl)-3- heptene F24tEC₂F₅CH═CHC(CF₃)₃ 1,1,1,2,2,6,6,6-octafluoro-5,5-bis(trifluoromethyl)-3-hexene F33E C₂F₅CF₂CH═CHCF₂C₂F₅1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluoro-4-octene F3i3iE(CF₃)₂CFCH═CHCF(CF₃)₂1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)-3- hexene F33iEC₂F₅CF₂CH═CHCF(CF₃)₂1,1,1,2,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)-3- heptene F16ECF₃CH═CH(CF₂)₅CF₃ 1,1,1,4,4,5,5,6,6,7,7,8,8,,9,9,9-hexadecafluoro-2-nonene F16sE CF₃CH═CHCF(CF₃)(CF₂)₂C₂F₅1,1,1,4,5,5,6,6,7,7,8,8,8-tridecafluoro-4- (trifluoromethyl)-2-hepteneF16tE CF₃CH═CHC(CF₃)₂CF₂C₂F₅1,1,1,6,6,6-octafluoro-4,4-bis(trifluoromethyl)-2-heptene F25EC₂F₅CH═CH(CF₂)₄CF₃ 1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoro-3-nonene F25iE C₂F₅CH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7- (trifluoromethyl)-3-octeneF25tE C₂F₅CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,6,6,7,7,7-decafluoro-5,5-bis(trifluoromethyl)-3- heptene F34EC₂F₅CF₂CH═CH—(CF₂)₃CF₃ 1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoro-4-nonene F34iE C₂F₅CF₂CH═CH—CF₂CF(CF₃)₂1,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7- (trifluoromethyl)-4-octeneF34sE C₂F₅CF₂CH═CHCF(CF₃)C₂F₅ 1,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6-(trifluoromethyl)-4-octene F34tE C₂F₅CF₂CH═CHC(CF₃)₃1,1,1,5,5,6,6,7,7,7-decafluoro-2,2-bis(trifluoromethyl)-3- heptene F3i4E(CF₃)₂CFCH═CH(CF₂)₃CF₃1,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro-2(trifluoromethyl)- 3-octeneF3i4iE (CF₃)₂CFCH═CHCF₂CF(CF₃)₂1,1,1,2,5,5,6,7,7,7-decafluoro-2,6-bis(trifluoromethyl)-3- hepteneF3i4sE (CF₃)₂CFCH═CHCF(CF₃)C₂F₅1,1,1,2,5,6,6,7,7,7-decafluoro-2,5-bis(trifluoromethyl)-3- hepteneF3i4tE (CF₃)₂CFCH═CHC(CF₃)₃1,1,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyl)-3- hexene F26EC₂F₅CH═CH(CF₂)₅CF₃1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-octadecafluoro-3- decene F26sEC₂F₅CH═CHCF(CF₃)(CF₂)₂C₂F₅1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5-(trifluoromethyl)-3-nonene F26tE C₂F₅CH═CHC(CF₃)₂—CF₂C₂F₅1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5- bis(trifluoromethyl)-3-octeneF35E C₂F₅CF₂CH═CH—(CF₂)₄CF₃1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluoro-4- decene F35iEC₂F₅CF₂CH═CHCF₂CF₂—CF(CF₃)₂1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8-(trifluoromethyl)-4-nonene F35tE C₂F₅CF₂CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6- bis(trifluoromethyl)-4-octeneF3i5E (CF₃)₂CFCH═CH—(CF₂)₄CF₃1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)-3-nonene F3i5iE (CF₃)₂CFCH═CHCF₂CF₂—CF(CF₃)₂1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7- bis(trifluoromethyl-3-octeneF3i5tE (CF₃)₂CFCH═CHC(CF₃)₂C₂F₅1,1,1,2,6,6,7,7,7-nonafluoro-2,5,5-tris(trifluoromethyl)- 3-heptene F44ECF₃(CF₂)₃CH═CH(CF₂)₃CF₃1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluoro-5- decene F44iECF₃(CF₂)₃CH═CH—CF₂CF(CF₃)₂1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)-4-nonene F44sE CF₃(CF₂)₃CH═CHCF(CF₃)C₂F₅1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3-(trifluoromethyl)-4-nonene F44tE CF₃(CF₂)₃CH═CHC(CF₃)₃1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2,- bis(trifluoromethyl)-3-octeneF4i4iE (CF₃)₂CFCF₂CH═CHCF₂CF—(CF₃)₂1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7- bis(trifluoromethyl)-4-octeneF4i4sE (CF₃)₂CFCF₂CH═CHCF(CF₃)—C₂F₅1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6- bis(trifluoromethyl)-4-octeneF4i4tE (CF₃)₂CFCF₂CH═CHC(CF₃)₃1,1,1,5,5,6,7,7,7-nonafluoro-2,2,6-tris(trifluoromethyl)- 3-hepteneF4s4sE C₂F₅CF(CF₃)CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6- bis(trifluoromethyl)-4-octeneF4s4tE C₂F₅CF(CF₃)CH═CH—C(CF₃)₃1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5-tris(trifluoromethyl)- 3-hepteneF4t4tE (CF₃)₃CCH═CH—C(CF₃)₃1,1,1,6,6,6-hexafluoro-2,2,5,5-tetrakis(trifluoromethyl)- 3-hexene

Compounds of Formula I may be prepared by contacting a perfluoroalkyliodide of the formula R¹I with a perfluoroalkyltrihydroolefin of theformula R²CH═CH₂ to form a trihydroiodoperfluoroalkane of the formulaR¹CH₂CHIR². This trihydroiodoperfluoroalkane can then bedehydroiodinated to form R¹CH═CHR². Alternatively, the olefin R¹CH═CHR²may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane ofthe formula R¹CHICH₂R² formed in turn by reacting a perfluoroalkyliodide of the formula R²I with a perfluoroalkyltrihydroolefin of theformula R¹CH═CH₂.

Said contacting of a perfluoroalkyl iodide with aperfluoroalkyltrihydroolefin may take place in batch mode by combiningthe reactants in a suitable reaction vessel capable of operating underthe autogenous pressure of the reactants and products at reactiontemperature. Suitable reaction vessels include fabricated from stainlesssteels, in particular of the austenitic type, and the well-known highnickel alloys such as Monel® nickel-copper alloys, Hastelloy® nickelbased alloys and Inconel® nickel-chromium alloys.

Alternatively, the reaction may take be conducted in semi-batch mode inwhich the perfluoroalkyltrihydroolefin reactant is added to theperfluoroalkyl iodide reactant by means of a suitable addition apparatussuch as a pump at the reaction temperature.

The ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefinshould be between about 1:1 to about 4:1, preferably from about 1.5:1 to2.5:1. Ratios less than 1.5:1 tend to result in large amounts of the 2:1adduct as reported by Jeanneaux, et. al. in Journal of FluorineChemistry, Vol. 4, pages 261-270 (1974).

Preferred temperatures for contacting of said perfluoroalkyl iodide withsaid perfluoroalkyltrihydroolefin are preferably within the range ofabout 150° C. to 300° C., preferably from about 170° C. to about 250°C., and most preferably from about 180° C. to about 230° C.

Suitable contact times for the reaction of the perfluoroalkyl iodidewith the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18hours, preferably from about 4 to about 12 hours.

The trihydroiodoperfluoroalkane prepared by reaction of theperfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be useddirectly in the dehydroiodination step or may preferably be recoveredand purified by distillation prior to the dehydroiodination step.

The dehydroiodination step is carried out by contacting thetrihydroiodoperfluoroalkane with a basic substance. Suitable basicsubstances include alkali metal hydroxides (e.g., sodium hydroxide orpotassium hydroxide), alkali metal oxide (for example, sodium oxide),alkaline earth metal hydroxides (e.g., calcium hydroxide), alkalineearth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g.,sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, ormixtures of basic substances such as soda lime. Preferred basicsubstances are sodium hydroxide and potassium hydroxide.

Said contacting of the trihydroiodoperfluoroalkane with a basicsubstance may take place in the liquid phase preferably in the presenceof a solvent capable of dissolving at least a portion of both reactants.Solvents suitable for the dehydroiodination step include one or morepolar organic solvents such as alcohols (e.g., methanol, ethanol,n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol),nitriles (e.g., acetonitrile, propionitrile, butyronitrile,benzonitrile, or adiponitrile), dimethyl sulfoxide,N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choiceof solvent may depend on the boiling point product and the ease ofseparation of traces of the solvent from the product duringpurification. Typically, ethanol or isopropanol are good solvents forthe reaction.

Typically, the dehydroiodination reaction may be carried out by additionof one of the reactants (either the basic substance or thetrihydroiodoperfluoroalkane) to the other reactant in a suitablereaction vessel. Said reaction may be fabricated from glass, ceramic, ormetal and is preferably agitated with an impeller or stirring mechanism.

Temperatures suitable for the dehydroiodination reaction are from about10° C. to about 100° C., preferably from about 20° C. to about 70° C.The dehydroiodination reaction may be carried out at ambient pressure orat reduced or elevated pressure. Of note are dehydroiodination reactionsin which the compound of Formula I is distilled out of the reactionvessel as it is formed.

Alternatively, the dehydroiodination reaction may be conducted bycontacting an aqueous solution of said basic substance with a solutionof the trihydroiodoperfluoroalkane in one or more organic solvents oflower polarity such as an alkane (e.g., hexane, heptane, or octane),aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g.,methylene chloride, chloroform, carbon tetrachloride, orperchloroethylene), or ether (e.g., diethyl ether, methyl tert-butylether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane,dimethoxyethane, diglyme, or tetraglyme) in the presence of a phasetransfer catalyst. Suitable phase transfer catalysts include quaternaryammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammoniumhydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammoniumchloride, and tricaprylylmethylammonium chloride), quaternaryphosphonium halides (e.g., triphenylmethylphosphonium bromide andtetraphenylphosphonium chloride), or cyclic polyether compounds known inthe art as crown ethers (e.g., 18-crown-6 and 15-crown-5).

Alternatively, the dehydroiodination reaction may be conducted in theabsence of solvent by adding the trihydroiodoperfluoroalkane to a solidor liquid basic substance.

Suitable reaction times for the dehydroiodination reactions are fromabout 15 minutes to about six hours or more depending on the solubilityof the reactants. Typically the dehydroiodination reaction is rapid andrequires about 30 minutes to about three hours for completion.

The compound of formula I may be recovered from the dehydroiodinationreaction mixture by phase separation after addition of water, bydistillation, or by a combination thereof.

In another embodiment of the present invention, fluoroolefins comprisecyclic fluoroolefins (cyclo-[CX═CY(CZW)_(n)—] (Formula II), wherein X,Y, Z, and W are independently selected from H and F, and n is an integerfrom 2 to 5). Representative cyclic fluoroolefins of Formula II arelisted in Table 2.

TABLE 2 Cyclic fluoroolefins Structure Chemical name FC-C1316cccyclo-CF₂CF₂CF═CF— 1,2,3,3,4,4- hexafluorocyclobutene HFC-cyclo-CF₂CF₂CH═CH— 3,3,4,4- C1334cc tetrafluorocyclobutene HFC-C1436cyclo-CF₂CF₂CF₂CH═CH— 3,3,4,4,5,5,- hexafluorocyclopentene FC-C1418ycyclo-CF₂CF═CFCF₂CF₂— 1,2,3,3,4,4,5,5- octafluorocyclopentene FC-C151-cyclo-CF₂CF═CFCF₂CF₂CF₂— 1,2,3,3,4,4,5,5,6,6- 10y decafluorocyclohexene

In another embodiment, fluoroolefins may comprise those compounds listedin Table 3.

TABLE 3 Name Structure Chemical name HFC-1225ye CF₃CF═CHF1,2,3,3,3-pentafluoro-1-propene HFC-1225zc CF₃CH═CF₂1,1,3,3,3-pentafluoro-1-propene HFC-1225yc CHF₂CF═CF₂1,1,2,3,3-pentafluoro-1-propene HFC-1234ye CHF₂CF═CHF1,2,3,3-tetrafluoro-1-propene HFC-1234yf CF₃CF═CH₂2,3,3,3-tetrafluoro-1-propene HFC-1234ze CF₃CH═CHF1,3,3,3-tetrafluoro-1-propene HFC-1234yc CH₂FCF═CF₂1,1,2,3-tetrafluoro-1-propene HFC-1234zc CHF₂CH═CF₂1,1,3,3-tetrafluoro-1-propene HFC-1243yf CHF₂CF═CH₂2,3,3-trifluoro-1-propene HFC-1243zf CF₃CH═CH₂ 3,3,3-trifluoro-1-propeneHFC-1243yc CH₃CF═CF₂ 1,1,2-trifluoro-1-propene HFC-1243zc CH₂FCH═CF₂1,1,3-trifluoro-1-propene HFC-1243ye CH₂FCF═CHF1,2,3-trifluoro-1-propene HFC-1243ze CHF₂CH═CHF1,3,3-trifluoro-1-propene FC-1318my CF₃CF═CFCF₃1,1,1,2,3,4,4,4-octafluoro-2-butene FC-1318cy CF₃CF₂CF═CF₂1,1,2,3,3,4,4,4-octafluoro-1-butene HFC-1327my CF₃CF═CHCF₃1,1,1,2,4,4,4-heptafluoro-2-butene HFC-1327ye CHF═CFCF₂CF₃1,2,3,3,4,4,4-heptafluoro-1-butene HFC-1327py CHF₂CF═CFCF₃1,1,1,2,3,4,4-heptafluoro-2-butene HFC-1327et (CF₃)₂C═CHF1,3,3,3-tetrafluoro-2- (trifluoromethyl)-1-propene HFC-1327czCF₂═CHCF₂CF₃ 1,1,3,3,4,4,4-heptafluoro-1-butene HFC-1327cye CF₂═CFCHFCF₃1,1,2,3,4,4,4-heptafluoro-1-butene HFC-1327cyc CF₂═CFCF₂CHF₂1,1,2,3,3,4,4-heptafluoro-1-butene HFC-1336yf CF₃CF₂CF═CH₂2,3,3,4,4,4-hexafluoro-1-butene HFC-1336ze CHF═CHCF₂CF₃1,3,3,4,4,4-hexafluoro-1-butene HFC-1336eye CHF═CFCHFCF₃1,2,3,4,4,4-hexafluoro-1-butene HFC-1336eyc CHF═CFCF₂CHF₂1,2,3,3,4,4-hexafluoro-1-butene HFC-1336pyy CHF₂CF═CFCHF₂1,1,2,3,4,4-hexafluoro-2-butene HFC-1336qy CH₂FCF═CFCF₃1,1,1,2,3,4-hexafluoro-2-butene HFC-1336pz CHF₂CH═CFCF₃1,1,1,2,4,4-hexafluoro-2-butene HFC-1336mzy CF₃CH═CFCHF₂1,1,1,3,4,4-hexafluoro-2-butene HFC-1336qc CF₂═CFCF₂CH₂F1,1,2,3,3,4-hexafluoro-1-butene HFC-1336pe CF₂═CFCHFCHF₂1,1,2,3,4,4-hexafluoro-1-butene HFC-1336ft CH₂═C(CF₃)₂3,3,3-trifluoro-2-(trifluoromethyl)-1- propene HFC-1345qz CH₂FCH═CFCF₃1,1,1,2,4-pentafluoro-2-butene HFC-1345mzy CF₃CH═CFCH₂F1,1,1,3,4-pentafluoro-2-butene HFC-1345fz CF₃CF₂CH═CH₂3,3,4,4,4-pentafluoro-1-butene HFC-1345mzz CHF₂CH═CHCF₃1,1,1,4,4-pentafluoro-2-butene HFC-1345sy CH₃CF═CFCF₃1,1,1,2,3-pentafluoro-2-butene HFC-1345fyc CH₂═CFCF₂CHF₂2,3,3,4,4-pentafluoro-1-butene HFC-1345pyz CHF₂CF═CHCHF₂1,1,2,4,4-pentafluoro-2-butene HFC-1345cyc CH₃CF₂CF═CF₂1,1,2,3,3-pentafluoro-1-butene HFC-1345pyy CH₂FCF═CFCHF₂1,1,2,3,4-pentafluoro-2-butene HFC-1345eyc CH₂FCF₂CF═CF₂1,2,3,3,4-pentafluoro-1-butene HFC-1345ctm CF₂═C(CF₃)(CH₃)1,1,3,3,3-pentafluoro-2-methyl-1- propene HFC-1345ftp CH₂═C(CHF₂)(CF₃)2-(difluoromethyl)-3,3,3-trifluoro-1- propene HFC1345fye CH₂═CFCHFCF₃2,3,4,4,4-pentafluoro-1-butene HFC-1345eyf CHF═CFCH₂CF₃1,2,4,4,4-pentafluoro-1-butene HFC-1345eze CHF═CHCHFCF₃1,3,4,4,4-pentafluoro-1-butene HFC-1345ezc CHF═CHCF₂CHF₂1,3,3,4,4-pentafluoro-1-butene HFC-1345eye CHF═CFCHFCHF₂1,2,3,4,4-pentafluoro-1-butene HFC-1354fzc CH₂═CHCF₂CHF₂3,3,4,4-tetrafluoro-1-butene HFC-1354ctp CF₂═C(CHF₂)(CH₃)1,1,3,3-tetrafluoro-2-methyl-1- propene HFC-1354etm CHF═C(CF₃)(CH₃)1,3,3,3-tetrafluoro-2-methyl-1- propene HFC-1354tfp CH₂═C(CHF₂)₂2-(difluoromethyl)-3,3-difluoro-1- propene HFC-1354my CF₃CF═CHCH₃1,1,1,2-tetrafluoro-2-butene HFC-1354mzy CH₃CF═CHCF₃1,1,1,3-tetrafluoro-2-butene FC-141-10myy CF₃CF═CFCF₂CF₃1,1,1,2,3,4,4,5,5,5-decafluoro-2- pentene FC-141-10cy CF₂═CFCF₂CF₂CF₃1,1,2,3,3,4,4,5,5,5-decafluoro-1- pentene HFC-1429mzt (CF₃)₂C═CHCF₃1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl)-2-butene HFC-1429myzCF₃CF═CHCF₂CF₃ 1,1,1,2,4,4,5,5,5-nonafluoro-2- pentene HFC-1429mzyCF₃CH═CFCF₂CF₃ 1,1,1,3,4,4,5,5,5-nonafluoro-2- pentene HFC-1429eycCHF═CFCF₂CF₂CF₃ 1,2,3,3,4,4,5,5,5-nonafluoro-1- pentene HFC-1429czcCF₂═CHCF₂CF₂CF₃ 1,1,3,3,4,4,5,5,5-nonafluoro-1- pentene HFC-1429cyccCF₂═CFCF₂CF₂CHF₂ 1,1,2,3,3,4,4,5,5-nonafluoro-1- pentene HFC-1429pyyCHF₂CF═CFCF₂CF₃ 1,1,2,3,4,4,5,5,5-nonafluoro-2- pentene HFC-1429myycCF₃CF═CFCF₂CHF₂ 1,1,1,2,3,4,4,5,5-nonafluoro-2- pentene HFC-1429myyeCF₃CF═CFCHFCF₃ 1,1,1,2,3,4,5,5,5-nonafluoro-2- pentene HFC-1429eyymCHF═CFCF(CF₃)₂ 1,2,3,4,4,4-hexafluoro-3- (trifluoromethyl)-1-buteneHFC-1429cyzm CF₂═CFCH(CF₃)₂ 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene HFC-1429mzt CF₃CH═C(CF₃)₂1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl)-2-butene HFC-1429czymCF₂═CHCF(CF₃)₂ 1,1,3,4,4,4-hexafluoro-3- (trifluoromethyl)-1-buteneHFC-1438fy CH₂═CFCF₂CF₂CF₃ 2,3,3,4,4,5,5,5-octafluoro-1- penteneHFC-1438eycc CHF═CFCF₂CF₂CHF₂ 1,2,3,3,4,4,5,5-octafluoro-1- penteneHFC-1438ftmc CH₂═C(CF₃)CF₂CF₃ 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene HFC-1438czzm CF₂═CHCH(CF₃)₂1,1,4,4,4-pentafluoro-3- (trifluoromethyl)-1-butene HFC-1438ezymCHF═CHCF(CF₃)₂ 1,3,4,4,4-pentafluoro-3- (trifluoromethyl)-1-buteneHFC-1438ctmf CF₂═C(CF₃)CH₂CF₃ 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene HFC-1447fzy (CF₃)₂CFCH═CH₂3,4,4,4-tetrafluoro-3- (trifluoromethyl)-1-butene HFC-1447fzCF₃CF₂CF₂CH═CH₂ 3,3,4,4,5,5,5-heptafluoro-1-pentene HFC-1447fyccCH₂═CFCF₂CF₂CHF₂ 2,3,3,4,4,5,5-heptafluoro-1-pentene HFC-1447czcfCF₂═CHCF₂CH₂CF₃ 1,1,3,3,5,5,5-heptafluoro-1-pentene HFC-1447mytmCF₃CF═C(CF₃)(CH₃) 1,1,1,2,4,4,4-heptafluoro-3-methyl- 2-buteneHFC-1447fyz CH₂═CFCH(CF₃)₂ 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene HFC-1447ezz CHF═CHCH(CF₃)₂1,4,4,4-tetrafluoro-3- (trifluoromethyl)-1-butene HFC-1447qztCH₂FCH═C(CF₃)₂ 1,4,4,4-tetrafluoro-2- (trifluoromethyl)-2-buteneHFC-1447syt CH₃CF═C(CF₃)₂ 2,4,4,4-tetrafluoro-2-(trifluoromethyl)-2-butene HFC-1456szt (CF₃)₂C═CHCH₃3-(trifluoromethyl)-4,4,4-trifluoro-2- butene HFC-1456szy CF₃CF₂CF═CHCH₃3,4,4,5,5,5-hexafluoro-2-pentene HFC-1456mstz CF₃C(CH₃)═CHCF₃1,1,1,4,4,4-hexafluoro-2-methyl-2- butene HFC-1456fzce CH₂═CHCF₂CHFCF₃3,3,4,5,5,5-hexafluoro-1-pentene HFC-1456ftmf CH₂═C(CF₃)CH₂CF₃4,4,4-trifluoro-2-(trifluoromethyl)-1- butene FC-151-12c CF₃(CF₂)₃CF═CF₂1,1,2,3,3,4,4,5,5,6,6,6- dodecafluoro-1-hexene (or perfluoro-1-hexene)FC-151-12mcy CF₃CF₂CF═CFCF₂CF₃ 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (or perfluoro-3-hexene) FC-151-12mmtt(CF₃)₂C═C(CF₃)₂ 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene FC-151-12mmzz (CF₃)₂CFCF═CFCF₃1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl)-2-penteneHFC-152-11mmtz (CF₃)₂C═CHC₂F₅ 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene HFC-152-11mmyyz (CF₃)₂CFCF═CHCF₃1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl)-2-pentene PFBECF₃CF₂CF₂CF₂CH═CH₂ 3,3,4,4,5,5,6,6,6-nonafluoro-1- (or HFC-1549fz)hexene (or perfluorobutylethylene) HFC-1549fztmm CH₂═CHC(CF₃)₃4,4,4-trifluoro-3,3- bis(trifluoromethyl)-1-butene HFC-1549mmtts(CF₃)₂C═C(CH₃)(CF₃) 1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene HFC-1549fycz CH₂═CFCF₂CH(CF₃)₂2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl)-1-pentene HFC-1549mytsCF₃CF═C(CH₃)CF₂CF₃ 1,1,1,2,4,4,5,5,5-nonafluoro-3- methyl-2-penteneHFC-1549mzzz CF₃CH═CHCH(CF₃)₂ 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene HFC-1558szy CF₃CF₂CF₂CF═CHCH₃3,4,4,5,5,6,6,6-octafluoro-2-hexene HFC-1558fzccc CH₂═CHCF₂CF₂CF₂CHF₂3,3,4,4,5,5,6,6-octafluoro-2-hexene HFC-1558mmtzc (CF₃)₂C═CHCF₂CH₃1,1,1,4,4-pentafluoro-2- (trifluoromethyl)-2-pentene HFC-1558ftmfCH₂═C(CF₃)CH₂C₂F₅ 4,4,5,5,5-pentafluoro-2- (trifluoromethyl)-1-penteneHFC-1567fts CF₃CF₂CF₂C(CH₃)═CH₂ 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene HFC-1567szz CF₃CF₂CF₂CH═CHCH₃4,4,5,5,6,6,6-heptafluoro-2-hexene HFC-1567fzfc CH₂═CHCH₂CF₂C₂F₅4,4,5,5,6,6,6-heptafluoro-1-hexene HFC-1567sfyy CF₃CF₂CF═CFC₂H₅1,1,1,2,2,3,4-heptafluoro-3-hexene HFC-1567fzfy CH₂═CHCH₂CF(CF₃)₂4,5,5,5-tetrafluoro-4- (trifluoromethyl)-1-pentene HFC-1567myzzmCF₃CF═CHCH(CF₃)(CH₃) 1,1,1,2,5,5,5-heptafluoro-4-methyl- 2-penteneHFC-1567mmtyf (CF₃)₂C═CFC₂H₅ 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene FC-161-14myy CF₃CF═CFCF₂CF₂C₂F₅1,1,1,2,3,4,4,5,5,6,6,7,7,7- tetradecafluoro-2-heptene FC-161-14mcyyCF₃CF₂CF═CFCF₂C₂F₅ 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene HFC-162-13mzy CF₃CH═CFCF₂CF₂C₂F₅1,1,1,3,4,4,5,5,6,6,7,7,7- tridecafluoro-2-heptene HFC162-13myzCF₃CF═CHCF₂CF₂C₂F₅ 1,1,1,2,4,4,5,5,6,6,7,7,7- tridecafluoro-2-hepteneHFC-162-13mczy CF₃CF₂CH═CFCF₂C₂F₅ 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene HFC-162-13mcyz CF₃CF₂CF═CHCF₂C₂F₅1,1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-heptene PEVE CF₂═CFOCF₂CF₃pentafluoroethyl trifluorovinyl ether PMVE CF₂═CFOCF₃ trifluoromethyltrifluorovinyl ether

The compounds listed in Table 2 and Table 3 are available commerciallyor may be prepared by processes known in the art or as described herein.

1,1,1,4,4-pentafluoro-2-butene may be prepared from1,1,1,2,4,4-hexafluorobutane (CHF₂CH₂CHFCF₃) by dehydrofluorination oversolid KOH in the vapor phase at room temperature. The synthesis of1,1,1,2,4,4-hexafluorobutane is described in U.S. Pat. No. 6,066,768,incorporated herein by reference.

1,1,1,4,4,4-hexafluoro-2-butene may be prepared from1,1,1,4,4,4-hexafluoro-2-iodobutane (CF₃CHICH₂CF₃) by reaction with KOHusing a phase transfer catalyst at about 60° C. The synthesis of1,1,1,4,4,4-hexafluoro-2-iodobutane may be carried out by reaction ofperfluoromethyl iodide (CF₃I) and 3,3,3-trifluoropropene (CF₃CH═CH₂) atabout 200° C. under autogenous pressure for about 8 hours.

3,4,4,5,5,5-hexafluoro-2-pentene may be prepared by dehydrofluorinationof 1,1,1,2,2,3,3-heptafluoropentane (CF₃CF₂CF₂CH₂CH₃) using solid KOH orover a carbon catalyst at 200-300° C. 1,1,1,2,2,3,3-heptafluoropentanemay be prepared by hydrogenation of 3,3,4,4,5,5,5-heptafluoro-1-pentene(CF₃CF₂CF₂CH═CH₂).

1,1,1,2,3,4-hexafluoro-2-butene may be prepared by dehydrofluorinationof 1,1,1,2,3,3,4-heptafluorobutane (CH₂FCF₂CHFCF₃) using solid KOH.

1,1,1,2,4,4-hexafluoro-2-butene may be prepared by dehydrofluorinationof 1,1,1,2,2,4,4-heptafluorobutane (CHF₂CH₂CF₂CF₃) using solid KOH.

1,1,1,3,4,4-hexafluoro2-butene may be prepared by dehydrofluorination of1,1,1,3,3,4,4-heptafluorobutane (CF₃CH₂CF₂CHF₂) using solid KOH.

1,1,1,2,4-pentafluoro-2-butene may be prepared by dehydrofluorination of1,1,1,2,2,3-hexafluorobutane (CH₂FCH₂CF₂CF₃) using solid KOH.

1,1,1,3,4-pentafluoro-2-butene may be prepared by dehydrofluorination of1,1,1,3,3,4-hexafluorobutane (CF₃CH₂CF₂CH₂F) using solid KOH.

1,1,1,3-tetrafluoro-2-butene may be prepared by reacting1,1,1,3,3-pentafluorobutane (CF₃CH₂CF₂CH₃) with aqueous KOH at 120° C.

1,1,1,4,4,5,5,5-octafluoro-2-pentene may be prepared from(CF₃CHICH₂CF₂CF₃) by reaction with KOH using a phase transfer catalystat about 60° C. The synthesis of4-iodo-1,1,1,2,2,5,5,5-octafluoropentane may be carried out by reactionof perfluoroethyliodide (CF₃CF₂I) and 3,3,3-trifluoropropene at about200° C. under autogenous pressure for about 8 hours.

1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene may be prepared from1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane (CF₃CF₂CHICH₂CF₂CF₃) byreaction with KOH using a phase transfer catalyst at about 60° C. Thesynthesis of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane may be carriedout by reaction of perfluoroethyliodide (CF₃CF₂I) and3,3,4,4,4-pentafluoro-1-butene (CF₃CF₂CH═CH₂) at about 200° C. underautogenous pressure for about 8 hours.

1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2-pentene may be preparedby the dehydrofluorination of1,1,1,2,5,5,5-heptafluoro-4-iodo-2-(trifluoromethyl)-pentane(CF₃CHICH₂CF(CF₃)₂) with KOH in isopropanol. CF₃CHICH₂CF(CF₃)₂ is madefrom reaction of (CF₃)₂CFI with CF₃CH═CH₂ at high temperature, such asabout 200° C.

1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene may be prepared by the reactionof 1,1,1,4,4,4-hexafluoro-2-butene (CF₃CH═CHCF₃) withtetrafluoroethylene (CF₂═CF₂) and antimony pentafluoride (SbF₅).

2,3,3,4,4-pentafluoro-1-butene may be prepared by dehydrofluorination of1,1,2,2,3,3-hexafluorobutane over fluorided alumina at elevatedtemperature.

2,3,3,4,4,5,5,5-octafluoro-1-pentene may be prepared bydehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane over solidKOH.

1,2,3,3,4,4,5,5-octafluoro-1-pentene may be prepared bydehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane overfluorided alumina at elevated temperature.

The compositions of the present invention may comprise a single compoundof Formula I, Formula II, or Table 3 or may comprise a combination ofsaid compounds. Additionally, many of the compounds of Formula I,Formula II, and Table 3 may exist as different configurational isomersor stereoisomers. The present invention is intended to include allsingle configurational isomers, single stereoisomers or any combinationthereof. For instance, 1,3,3,3-tetrafluoropropene (HFC-1234ze) is meantto represent the E-isomer, Z-isomer, or any combination or mixture ofboth isomers in any ratio. Another example is F12E, by which isrepresented the E-isomer, Z-isomer, or any combination or mixture ofboth isomers in any ratio.

Compositions of the present invention have zero or low ozone depletionpotential and low global warming potential (GWP). The fluoroolefins ofthe present invention or mixtures of fluoroolefins of this inventionwith other refrigerants will have global warming potentials that areless than many hydrofluorocarbon refrigerants currently in use. Oneaspect of the present invention is to provide a refrigerant with aglobal warming potential of less than 1000, less than 500, less than150, less than 100, or less than 50. Another aspect of the presentinvention is to reduce the net GWP of refrigerant mixtures by addingfluoroolefins to said mixtures.

The compositions of the present invention that are combinations ormixtures may be prepared by any convenient method to combine the desiredamounts of the individual components. A preferred method is to weigh thedesired component amounts and thereafter combine the components in anappropriate vessel. Agitation may be used, if desired.

An alternative means for making compositions of the present inventioncomprises (i) reclaiming a volume of one or more components of arefrigerant composition from at least one refrigerant container, (ii)removing impurities sufficiently to enable reuse of said one or more ofthe reclaimed components, (iii) and optionally, combining all or part ofsaid reclaimed volume of components with at least one additionalrefrigerant composition or component.

A refrigerant container may be any container in which is stored arefrigerant blend composition that has been used in a refrigerationapparatus, air-conditioning apparatus or heat pump apparatus. Saidrefrigerant container may be the refrigeration apparatus,air-conditioning apparatus or heat pump apparatus in which therefrigerant blend was used. Additionally, the refrigerant container maybe a storage container for collecting reclaimed refrigerant blendcomponents, including but not limited to pressurized gas cylinders.

Residual refrigerant means any amount of refrigerant blend orrefrigerant blend component that may be moved out of the refrigerantcontainer by any method known for transferring refrigerant blends orrefrigerant blend components.

Impurities may be any component that is in the refrigerant blend orrefrigerant blend component due to its use in a refrigeration apparatus,air-conditioning apparatus or heat pump apparatus. Such impuritiesinclude but are not limited to refrigeration lubricants, being thosedescribed earlier herein, particulates such as metal or elastomer thatmay have come out of the refrigeration apparatus, air-conditioningapparatus or heat pump apparatus, and any other contaminants that mayadversely effect the performance of the refrigerant blend composition.

Such impurities may be removed sufficiently to allow reuse of therefrigerant blend or refrigerant blend component without adverselyeffecting the performance or equipment within which the refrigerantblend or refrigerant blend component will be used.

It may be necessary to provide additional refrigerant blend orrefrigerant blend component to the residual refrigerant blend orrefrigerant blend component in order to produce a composition that meetsthe specifications required for a given product. For instance, if arefrigerant blend has 3 components in a particular weight percentagerange, it may be necessary to add one or more of the components in agiven amount in order to restore the composition to within thespecification limits.

The compositions of the present invention that are useful asrefrigerants or heat transfer fluids comprise at least one fluoroolefinselected from the group consisting of:

-   -   (i) fluoroolefins of the formula E- or Z-R¹CH═CHR², wherein R¹        and R² are, independently, C₁ to C₆ perfluoroalkyl groups, and        wherein the total number of carbons in the compound is at least        5;    -   (ii) cyclic fluoroolefins of the formula        cyclo-[CX═CY(CZW)_(n)—], wherein X, Y, Z, and W, independently,        are H or F, and n is an integer from 2 to 5; and    -   (iii) fluoroolefins selected from the group consisting of:        -   1,2,3,3,3-pentafluoro-1-propene (CF₃CF═CHF);            1,1,3,3,3-pentafluoro-1-propene (CF₃CH═CF₂);            1,1,2,3,3-pentafluoro-1-propene (CHF₂CF═CF₂);            1,2,3,3-tetrafluoro-1-propene (CHF₂CF═CHF);            2,3,3,3-tetrafluoro-1-propene (CF₃CF═CH₂);            1,1,2,3-tetrafluoro-1-propene (CH₂FCF═CF₂);            1,1,3,3-tetrafluoro-1-propene (CHF₂CH═CF₂);            2,3,3-trifluoro-1-propene (CHF₂CF═CH₂);            3,3,3-trifluoro-1-propene (CF₃CH═CH₂);            1,1,2-trifluoro-1-propene (CH₃CF═CF₂);            1,2,3-trifluoro-1-propene (CH₂FCF═CF₂);            1,1,3-trifluoro-1-propene (CH₂FCH═CF₂);            1,3,3-trifluoro-1-propene (CHF₂CH═CHF);            1,1,1,2,3,4,4,4-octafluoro-2-butene (CF₃CF═CFCF₃);            1,1,2,3,3,4,4,4-octafluoro-1-butene (CF₃CF₂CF═CF₂);            1,1,1,2,4,4,4-heptafluoro-2-butene (CF₃CF═CHCF₃);            1,2,3,3,4,4,4-heptafluoro-1-butene (CHF═CFCF₂CF₃);            1,1,1,2,3,4,4-heptafluoro-2-butene (CHF₂CF═CFCF₃);            1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene            ((CF₃)₂C═CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene            (CF₂═CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene            (CF₂═CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene            (CF₂═CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene            (CF₃CF₂CF═CH₂); 1,3,3,4,4,4-hexafluoro-1-butene            (CHF═CHCF₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene            (CHF═CFCHFCF₃); 1,2,3,3,4,4-hexafluoro-1-butene            (CHF═CFCF₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene            (CHF₂CF═CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene            (CH₂FCF═CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene            (CHF₂CH═CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene            (CF₃CH═CFCHF₂); 1,1,2,3,3,4-hexafluoro-1-butene            (CF₂═CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene            (CF₂═CFCHFCHF₂);            3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH₂═C(CF₃)₂);            1,1,1,2,4-pentafluoro-2-butene (CH₂FCH═CFCF₃);            1,1,1,3,4-pentafluoro-2-butene (CF₃CH═CFCH₂F);            3,3,4,4,4-pentafluoro-1-butene (CF₃CF₂CH═CH₂);            1,1,1,4,4-pentafluoro-2-butene (CHF₂CH═CHCF₃);            1,1,1,2,3-pentafluoro-2-butene (CH₃CF═CFCF₃);            2,3,3,4,4-pentafluoro-1-butene (CH₂═CFCF₂CHF₂);            1,1,2,4,4-pentafluoro-2-butene (CHF₂CF═CHCHF₂);            1,1,2,3,3-pentafluoro-1-butene (CH₃CF₂CF═CF₂);            1,1,2,3,4-pentafluoro-2-butene (CH₂FCF═CFCHF₂);            1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF₂═C(CF₃)(CH₃));            2-(difluoromethyl)-3,3,3-trifluoro-1-propene            (CH₂═C(CHF₂)(CF₃)); 2,3,4,4,4-pentafluoro-1-butene            (CH₂═CFCHFCF₃); 1,2,4,4,4-pentafluoro-1-butene            (CHF═CFCH₂CF₃); 1,3,4,4,4-pentafluoro-1-butene            (CHF═CHCHFCF₃); 1,3,3,4,4-pentafluoro-1-butene            (CHF═CHCF₂CHF₂); 1,2,3,4,4-pentafluoro-1-butene            (CHF═CFCHFCHF₂); 3,3,4,4-tetrafluoro-1-butene            (CH₂═CHCF₂CHF₂); 1,1-difluoro-2-(difluoromethyl)-1-propene            (CF₂═C(CHF₂)(CH₃)); 1,3,3,3-tetrafluoro-2-methyl-1-propene            (CHF═C(CF₃)(CH₃)); 3,3-difluoro-2-(difluoromethyl)-1-propene            (CH₂═C(CHF₂)₂); 1,1,1,2-tetrafluoro-2-butene (CF₃CF═CHCH₃);            1,1,1,3-tetrafluoro-2-butene (CH₃CF═CHCF₃);            1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF₃CF═CFCF₂CF₃);            1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF₂═CFCF₂CF₂CF₃);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene            ((CF₃)₂C═CHCF₃); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene            (CF₃CF═CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene            (CF₃CH═CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene            (CHF═CFCF₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene            (CF₂═CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene            (CF₂═CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene            (CHF₂CF═CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene            (CF₃CF═CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene            (CF₃CF═CFCHFCF₃);            1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CHF═CFCF(CF₃)₂);            1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CFCH(CF₃) 2);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene            (CF₃CH═C(CF₃)₂);            1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CHCF(CF₃)₂); 2,3,3,4,4,5,5,5-octafluoro-1-pentene            (CH₂═CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene            (CHF═CFCF₂CF₂CHF₂);            3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene            (CH₂═C(CF₃)CF₂CF₃);            1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CHCH(CF₃)₂);            1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene            (CHF═CHCF(CF₃)₂);            1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene            (CF₂═C(CF₃)CH₂CF₃);            3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            ((CF₃)₂CFCH═CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene            (CF₃CF₂CF₂CH═CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene            (CH₂═CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene            (CF₂═CHCF₂CH₂CF₃);            1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene            (CF₃CF═C(CF₃)(CH₃));            2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            (CH₂═CFCH(CF₃)₂);            1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            (CHF═CHCH(CF₃)₂);            1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene            (CH₂FCH═C(CF₃)₂);            1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene            (CH₃CF═C(CF₃)₂);            1,1,1-trifluoro-2-(trifluoromethyl)-2-butene            ((CF₃)₂C═CHCH₃); 3,4,4,5,5,5-hexafluoro-2-pentene            (CF₃CF₂CF═CHCH₃); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene            (CF₃C(CH₃)═CHCF₃); 3,3,4,5,5,5-hexafluoro-1-pentene            (CH₂═CHCF₂CHFCF₃);            4,4,4-trifluoro-3-(trifluoromethyl)-1-butene            (CH₂═C(CF₃)CH₂CF₃);            1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene            (CF₃(CF₂)₃CF═CF₂);            1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene            (CF₃CF₂CF═CFCF₂CF₃);            1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene            ((CF₃)₂C═C(CF₃)₂);            1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene            ((CF₃)₂CFCF═CFCF₃);            1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene            ((CF₃)₂C═CHC₂F₅);            1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene            ((CF₃)₂CFCF═CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene            (CF₃CF₂CF₂CF₂CH═CH₂);            4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene            (CH₂═CHC(CF₃)₃);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene            ((CF₃)₂C═C(CH₃)(CF₃));            2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene            (CH₂═CFCF₂CH(CF₃)₂);            1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene            (CF₃CF═C(CH₃)CF₂CF₃);            1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene            (CF₃CH═CHCH(CF₃)₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene            (CF₃CF₂CF₂CF═CHCH₃); 3,3,4,4,5,5,6,6-octafluoro1-hexene            (CH₂═CHCF₂CF₂CF₂CHF₂);            1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene            ((CF₃)₂C═CHCF₂CH₃);            4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene            (CH₂═C(CF₃)CH₂C₂F₅);            3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene            (CF₃CF₂CF₂C(CH₃)═CH₂); 4,4,5,5,6,6,6-heptafluoro-2-hexene            (CF₃CF₂CF₂CH═CHCH₃); 4,4,5,5,6,6,6-heptafluoro-1-hexene            (CH₂═CHCH₂CF₂C₂F₅); 1,1,1,2,2,3,4-heptafluoro-3-hexene            (CF₃CF₂CF═CFC₂H₅);            4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene            (CH₂═CHCH₂CF(CF₃)₂);            1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene            (CF₃CF═CHCH(CF₃)(CH₃));            1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene            ((CF₃)₂C═CFC₂H₅);            1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene            (CF₃CF═CFCF₂CF₂C₂F₅);            1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene            (CF₃CF₂CF═CFCF₂C₂F₅);            1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene            (CF₃CH═CFCF₂CF₂C₂F₅);            1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene            (CF₃CF═CHCF₂CF₂C₂F₅);            1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene            (CF₃CF₂CH═CFCF₂C₂F₅);            1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene            (CF₃CF₂CF═CHCF₂C₂F₅); CF₂═CFOCF₂CF₃ (PEVE) and CF₂═CFOCF₃            (PMVE).

The present invention further relates to compositions comprising atleast one fluoroolefin and at least one flammable refrigerant or heattransfer fluid, wherein the fluoroolefin is selected from the groupconsisting of:

-   -   (i) fluoroolefins of the formula E- or Z-R¹CH═CHR², wherein R¹        and R² are, independently, C₁ to C₆ perfluoroalkyl groups, and        wherein the total number of carbons in the compound is at least        5;    -   (ii) cyclic fluoroolefins of the formula        cyclo-[CX═CY(CZW)_(n)—], wherein X, Y, Z, and W, independently,        are H or F, and n is an integer from 2 to 5; and    -   (iii) fluoroolefins selected from the group consisting of:        -   1,2,3,3,3-pentafluoro-1-propene (CF₃CF═CHF);            1,1,3,3,3-pentafluoro-1-propene (CF₃CH═CF₂);            1,1,2,3,3-pentafluoro-1-propene (CHF₂CF═CF₂);            1,2,3,3-tetrafluoro-1-propene (CHF₂CF═CHF);            2,3,3,3-tetrafluoro-1-propene (CF₃CF═CH₂);            1,1,2,3-tetrafluoro-1-propene (CH₂FCF═CF₂);            1,1,3,3-tetrafluoro-1-propene (CHF₂CH═CF₂);            2,3,3-trifluoro-1-propene (CHF₂CF═CH₂);            3,3,3-trifluoro-1-propene (CF₃CH═CH₂);            1,1,2-trifluoro-1-propene (CH₃CF═CF₂);            1,2,3-trifluoro-1-propene (CH₂FCF═CF₂);            1,1,3-trifluoro-1-propene (CH₂FCH═CF₂);            1,3,3-trifluoro-1-propene (CHF₂CH═CHF);            1,1,1,2,3,4,4,4-octafluoro-2-butene (CF₃CF═CFCF₃);            1,1,2,3,3,4,4,4-octafluoro-1-butene (CF₃CF₂CF═CF₂);            1,1,1,2,4,4,4-heptafluoro-2-butene (CF₃CF═CHCF₃);            1,2,3,3,4,4,4-heptafluoro-1-butene (CHF═CFCF₂CF₃);            1,1,1,2,3,4,4-heptafluoro-2-butene (CHF₂CF═CFCF₃);            1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene            ((CF₃)₂C═CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene            (CF₂═CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene            (CF₂═CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene            (CF₂═CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene            (CF₃CF₂CF═CH₂); 1,3,3,4,4,4-hexafluoro-1-butene            (CHF═CHCF₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene            (CHF═CFCHFCF₃); 1,2,3,3,4,4-hexafluoro-1-butene            (CHF═CFCF₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene            (CHF₂CF═CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene            (CH₂FCF═CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene            (CHF₂CH═CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene            (CF₃CH═CFCHF₂); 1,1,2,3,3,4-hexafluoro-1-butene            (CF₂═CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene            (CF₂═CFCHFCHF₂);            3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH₂═C(CF₃)₂);            1,1,1,2,4-pentafluoro-2-butene (CH₂FCH═CFCF₃);            1,1,1,3,4-pentafluoro-2-butene (CF₃CH═CFCH₂F);            3,3,4,4,4-pentafluoro-1-butene (CF₃CF₂CH═CH₂);            1,1,1,4,4-pentafluoro-2-butene (CHF₂CH═CHCF₃);            1,1,1,2,3-pentafluoro-2-butene (CH₃CF═CFCF₃);            2,3,3,4,4-pentafluoro-1-butene (CH₂═CFCF₂CHF₂);            1,1,2,4,4-pentafluoro-2-butene (CHF₂CF═CHCHF₂);            1,1,2,3,3-pentafluoro-1-butene (CH₃CF₂CF═CF₂);            1,1,2,3,4-pentafluoro-2-butene (CH₂FCF═CFCHF₂);            1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF₂═C(CF₃)(CH₃));            2-(difluoromethyl)-3,3,3-trifluoro-1-propene            (CH₂═C(CHF₂)(CF₃)); 2,3,4,4,4-pentafluoro-1-butene            (CH₂═CFCHFCF₃); 1,2,4,4,4-pentafluoro-1-butene            (CHF═CFCH₂CF₃); 1,3,4,4,4-pentafluoro-1-butene            (CHF═CHCHFCF₃); 1,3,3,4,4-pentafluoro-1-butene            (CHF═CHCF₂CHF₂); 1,2,3,4,4-pentafluoro-1-butene            (CHF═CFCHFCHF₂); 3,3,4,4-tetrafluoro-1-butene            (CH₂═CHCF₂CHF₂); 1,1-difluoro-2-(difluoromethyl)-1-propene            (CF₂═C(CHF₂)(CH₃)); 1,3,3,3-tetrafluoro-2-methyl-1-propene            (CHF═C(CF₃)(CH₃)); 3,3-difluoro-2-(difluoromethyl)-1-propene            (CH₂═C(CHF₂)₂); 1,1,1,2-tetrafluoro-2-butene (CF₃CF═CHCH₃);            1,1,1,3-tetrafluoro-2-butene (CH₃CF═CHCF₃);            1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF₃CF═CFCF₂CF₃);            1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF₂═CFCF₂CF₂CF₃);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene            ((CF₃)₂C═CHCF₃); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene            (CF₃CF═CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene            (CF₃CH═CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene            (CHF═CFCF₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene            (CF₂═CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene            (CF₂═CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene            (CHF₂CF═CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene            (CF₃CF═CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene            (CF₃CF═CFCHFCF₃);            1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CHF═CFCF(CF₃)₂);            1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CFCH(CF₃) 2);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene            (CF₃CH═C(CF₃)₂);            1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CHCF(CF₃)₂); 2,3,3,4,4,5,5,5-octafluoro-1-pentene            (CH₂═CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene            (CHF═CFCF₂CF₂CHF₂);            3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene            (CH₂═C(CF₃)CF₂CF₃);            1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CHCH(CF₃)₂);            1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene            (CHF═CHCF(CF₃)₂);            1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene            (CF₂═C(CF₃)CH₂CF₃);            3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            ((CF₃)₂CFCH═CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene            (CF₃CF₂CF₂CH═CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene            (CH₂═CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene            (CF₂═CHCF₂CH₂CF₃);            1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene            (CF₃CF═C(CF₃)(CH₃));            2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            (CH₂═CFCH(CF₃)₂);            1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            (CHF═CHCH(CF₃)₂);            1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene            (CH₂FCH═C(CF₃)₂);            1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene            (CH₃CF═C(CF₃)₂);            1,1,1-trifluoro-2-(trifluoromethyl)-2-butene            ((CF₃)₂C═CHCH₃); 3,4,4,5,5,5-hexafluoro-2-pentene            (CF₃CF₂CF═CHCH₃); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene            (CF₃C(CH₃)═CHCF₃); 3,3,4,5,5,5-hexafluoro-1-pentene            (CH₂═CHCF₂CHFCF₃);            4,4,4-trifluoro-3-(trifluoromethyl)-1-butene            (CH₂═C(CF₃)CH₂CF₃);            1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene            (CF₃(CF₂)₃CF═CF₂);            1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene            (CF₃CF₂CF═CFCF₂CF₃);            1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene            ((CF₃)₂C═C(CF₃)₂);            1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene            ((CF₃)₂CFCF═CFCF₃);            1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene            ((CF₃)₂C═CHC₂F₅);            1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene            ((CF₃)₂CFCF═CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene            (CF₃CF₂CF₂CF₂CH═CH₂);            4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene            (CH₂═CHC(CF₃)₃);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene            ((CF₃)₂C═C(CH₃)(CF₃));            2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene            (CH₂═CFCF₂CH(CF₃)₂);            1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene            (CF₃CF═C(CH₃)CF₂CF₃);            1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene            (CF₃CH═CHCH(CF₃)₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene            (CF₃CF₂CF₂CF═CHCH₃); 3,3,4,4,5,5,6,6-octafluoro1-hexene            (CH₂═CHCF₂CF₂CF₂CHF₂);            1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene            ((CF₃)₂C═CHCF₂CH₃);            4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene            (CH₂═C(CF₃)CH₂C₂F₅);            3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene            (CF₃CF₂CF₂C(CH₃)═CH₂); 4,4,5,5,6,6,6-heptafluoro-2-hexene            (CF₃CF₂CF₂CH═CHCH₃); 4,4,5,5,6,6,6-heptafluoro-1-hexene            (CH₂═CHCH₂CF₂C₂F₅); 1,1,1,2,2,3,4-heptafluoro-3-hexene            (CF₃CF₂CF═CFC₂H₅);            4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene            (CH₂═CHCH₂CF(CF₃)₂);            1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene            (CF₃CF═CHCH(CF₃)(CH₃));            1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene            ((CF₃)₂C═CFC₂H₅);            1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene            (CF₃CF═CFCF₂CF₂C₂F₅);            1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene            (CF₃CF₂CF═CFCF₂C₂F₅);            1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene            (CF₃CH═CFCF₂CF₂C₂F₅);            1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene            (CF₃CF═CHCF₂CF₂C₂F₅);            1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene            (CF₃CF₂CH═CFCF₂C₂F₅);            1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene            (CF₃CF₂CF═CHCF₂C₂F₅); CF₂═CFOCF₂CF₃ (PEVE) and CF₂═CFOCF₃            (PMVE).

Of particular utility in compositions comprising at least one flammablerefrigerant and at least one fluoroolefin are those fluoroolefins thatthemselves are non-flammable. Flammability of a fluoroolefin appears tobe related to the numbers of fluorine atoms and the numbers of hydrogenatoms in the molecule. The equation below provides a flammability factorthat may be calculated as an indication of predicted flammability:

${{flammability}\mspace{14mu}{factor}} = \frac{F}{\left( {F + H} \right)}$

wherein:

-   -   F=the number of fluorine atoms; and    -   H=the number of hydrogen atoms in a molecule.

As certain compounds have been experimentally determined to beflammable, the cut-off for non-flammable fluoroolefin flammabilityfactors has been determined. Fluoroolefins may be determined to beflammable or non-flammable by testing under conditions specified byASHRAE (American Society of Heating, Refrigerating and Air-ConditioningEngineers, Inc.) Standard 34-2001, under ASTM (American Society ofTesting and Materials) E681-01, with an electronic ignition source. Suchtests of flammability are conducted with the compound of interest at 101kPa (14.7 psia) and a specified temperature (often 100° C. (212° F.)) atvarious concentrations in air in order to determine the lowerflammability limit (LFL) and/or upper flammability limit (UFL) of thetest compound in air.

The flammability factors for several fluoroolefins are listed in Table 4along with the experimental determination of flammable or non-flammable.Therefore, it can be predicted for the other fluoroolefins of thepresent disclosure, which will be most useful in combination with theflammable refrigerants of the present disclosure as being in factnon-flammable fluoroolefins.

TABLE 4 Experimental Prediction from Flammability flammability CompoundFormula #F #H F/(F + H) (LFL, vol % in air) factor HFC- C₃HF₅ 5 1 0.83non-flammable non-flammable 1225ye HFC-1234yf C₃H₂F₄ 4 2 0.67 6.0flammable E-HFC- C₃H₂F₄ 4 2 0.67 5.0 flammable 1234ze HFC- C₅HF₉ 9 10.90 non-flammable non-flammable 1429myz/mzy (mixture of isomers) F12EC₆H₂F₈ 8 2 0.75 non-flammable non-flammable Other fluoroolefins HFC-1243C₃H₃F₃ 3 3 0.15 na Flammable FC-1318 C₄F₈ 8 0 1.0 na non-flammableHFC-1327 C₄HF₇ 7 1 0.88 na non-flammable HFC-1336 C₄H₂F₆ 6 2 0.75 nanon-flammable HFC-1345 C₄H₃F₅ 5 3 0.63 na flammable HFC-1354 C₄H₄F₄ 4 40.50 na flammable FC-141-10 C₅F₁₀ 10 0 1.0 na non-flammable HFC-1429C₅HF₉ 9 1 0.90 na non-flammable HFC-1438 C₅H₂F₈ 8 2 0.80 nanon-flammable HFC-1447 C₅H₃F₇ 7 3 0.70 na non-flammable HFC-1456 C₅H₄F₆6 4 0.6 na flammable FC-151-12 C₆F₁₂ 12 0 1.0 na non-flammableHFC-152-11 C₆HF₁₁ 11 1 0.92 na non-flammable HFC-153-10 C₆H₂F₁₀ 10 20.83 na non-flammable HFC-1549 C₆H₃F₉ 9 3 0.75 na non-flammable HFC-1558C₆H₄F₈ 8 4 0.67 na flammable HFC-1567 C₆H₅F₇ 7 5 0.58 na flammableFC-161-14 C₇F₁₄ 14 0 1.0 na non-flammable HFC-162-13 C₇HF₁₃ 13 1 0.93 nanon-flammable HFC-163-12 C₇H₂F₁₂ 12 2 0.86 na non-flammable HFC-164-11C₇H₃F₁₁ 11 3 0.79 na non-flammable HFC-165-10 C₇H₄F₁₀ 10 4 0.71 nanon-flammable HFC-1669 C₇H₅F₉ 9 5 0.64 na flammable HFC-C1316 C₄F₆ 6 01.0 na non-flammable HFC-C1418 C₅F₈ 8 0 1.0 na non-flammable HFC-C151-10C₆F₁₀ 10 0 1.0 na non-flammable HFC-C1334 C₄H₂F₄ 4 2 0.67 na flammableHFC-C1436 C₅H₂F₆ 6 2 0.75 na non-flammable

The fluoroolefins as listed in Table 4 may be determined to be flammableor non-flammable based upon the value of the flammability factor. If theflammability factor is found to be equal to or greater than 0.70, thenthe fluoroolefin may be expected to be non-flammable. If theflammability factor is less than 0.70, then the fluoroolefin may beexpected to be flammable.

In another embodiment of the present invention, the fluoroolefins foruse in compositions with flammable refrigerants are those fluoroolefinsselected from the group consisting of:

-   -   (a) fluoroolefins of the formula E- or Z-R¹CH═CHR², wherein R¹        and R² are, independently, C₁ to C₆ perfluoroalkyl groups;    -   (b) cyclic fluoroolefins of the formula cyclo-[CX═CY(CZW)_(n)—],        wherein X, Y, Z, and W, independently, are H or F, and n is an        integer from 2 to 5, and wherein the flammability factor is        greater than or equal to 0.70; and    -   (c) fluoroolefins selected from the group consisting of:        -   1,2,3,3,3-pentafluoro-1-propene (CF₃CF═CHF);            1,1,3,3,3-pentafluoro-1-propene (CF₃CH═CF₂);            1,1,2,3,3-pentafluoro-1-propene (CHF₂CF═CF₂);            1,1,1,2,3,4,4,4-octafluoro-2-butene (CF₃CF═CFCF₃);            1,1,2,3,3,4,4,4-octafluoro-1-butene (CF₃CF₂CF═CF₂);            1,1,1,2,4,4,4-heptafluoro-2-butene (CF₃CF═CHCF₃);            1,2,3,3,4,4,4-heptafluoro-1-butene (CHF═CFCF₂CF₃);            1,1,1,2,3,4,4-heptafluoro-2-butene (CHF₂CF═CFCF₃);            1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene            ((CF₃)₂C═CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene            (CF₂═CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene            (CF₂═CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene            (CF₂═CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene            (CF₃CF₂CF═CH₂); 1,3,3,4,4,4-hexafluoro-1-butene            (CHF═CHCF₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene            (CHF═CFCHFCF₃); 1,2,3,3,4,4-hexafluoro-1-butene            (CHF═CFCF₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene            (CHF₂CF═CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene            (CH₂FCF═CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene            (CHF₂CH═CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene            (CF₃CH═CFCHF₂); 1,1,2,3,3,4-hexafluoro-1-butene            (CF₂═CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene            (CF₂═CFCHFCHF₂);            3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH₂═C(CF₃)₂);            1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF₃CF═CFCF₂CF₃);            1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF₂═CFCF₂CF₂CF₃);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene            ((CF₃)₂C═CHCF₃); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene            (CF₃CF═CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene            (CF₃CH═CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene            (CHF═CFCF₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene            (CF₂═CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene            (CF₂═CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene            (CHF₂CF═CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene            (CF₃CF═CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene            (CF₃CF═CFCHFCF₃);            1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CHF═CFCF(CF₃)₂);            1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CFCH(CF₃) 2);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene            (CF₃CH═C(CF₃)₂);            1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CHCF(CF₃)₂); 2,3,3,4,4,5,5,5-octafluoro-1-pentene            (CH₂═CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene            (CHF═CFCF₂CF₂CHF₂);            3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene            (CH₂═C(CF₃)CF₂CF₃);            1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CHCH(CF₃)₂);            1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene            (CHF═CHCF(CF₃)₂);            1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene            (CF₂═C(CF₃)CH₂CF₃);            3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            ((CF₃)₂CFCH═CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene            (CF₃CF₂CF₂CH═CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene            (CH₂═CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene            (CF₂═CHCF₂CH₂CF₃);            1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene            (CF₃CF═C(CF₃)(CH₃));            2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            (CH₂═CFCH(CF₃)₂);            1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            (CHF═CHCH(CF₃)₂);            1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene            (CH₂FCH═C(CF₃)₂);            1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene            (CH₃CF═C(CF₃)₂);            1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene            (CF₃(CF₂)₃CF═CF₂);            1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene            (CF₃CF₂CF═CFCF₂CF₃);            1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene            ((CF₃)₂C═C(CF₃)₂);            1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene            ((CF₃)₂CFCF═CFCF₃);            1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene            ((CF₃)₂C═CHC₂F₅);            1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene            ((CF₃)₂CFCF═CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene            (CF₃CF₂CF₂CF₂CH═CH₂);            4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene            (CH₂═CHC(CF₃)₃);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene            ((CF₃)₂C═C(CH₃)(CF₃));            2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene            (CH₂═CFCF₂CH(CF₃)₂);            1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene            (CF₃CF═C(CH₃)CF₂CF₃);            1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene            (CF₃CH═CHCH(CF₃)₂);            1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene            (CF₃CF═CFCF₂CF₂C₂F₅);            1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene            (CF₃CF₂CF═CFCF₂C₂F₅);            1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene            (CF₃CH═CFCF₂CF₂C₂F₅);            1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene            (CF₃CF═CHCF₂CF₂C₂F₅);            1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene            (CF₃CF₂CH═CFCF₂C₂F₅); and            1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene            (CF₃CF₂CF═CHCF₂C₂F₅).

In yet another embodiment, the fluoroolefins of the present disclosurethat may be particularly useful in combination with flammablerefrigerants, may be at least one fluoroolefin selected from the groupconsisting of:

-   -   (a) fluoroolefins of the formula E- or Z-R¹CH═CHR², wherein R¹        and R² are, independently, C₁ to C₆ perfluoroalkyl groups, and        wherein the flammability factor is greater than or equal to        0.70; and    -   (b) cyclic fluoroolefins of the formula cyclo-[CX═CY(CZW)_(n)—],        wherein X, Y, Z, and W, independently, are H or F, and n is an        integer from 2 to 5, and wherein the flammability factor is        greater than or equal to 0.70.

While the flammability factor provides a basis for predictingflammability of certain fluoroolefin compounds, there may be certainvariables, such as position of the hydrogen atoms on the molecule thatwould account for certain isomers with a given molecular formula beingflammable while other isomers are non-flammable. Therefore, theflammability factor may only be used as a tool for predictingflammability characteristics.

Flammable refrigerants of the present invention comprise any compound,which may be demonstrated to propagate a flame under specifiedconditions of temperature, pressure and composition when mixed with air.Flammable refrigerants may be identified by testing under conditionsspecified by ASHRAE (American Society of Heating, Refrigerating andAir-Conditioning Engineers, Inc.) Standard 34-2001, under ASTM (AmericanSociety of Testing and Materials) E681-01, with an electronic ignitionsource. Such tests of flammability are conducted with the refrigerant at101 kPa (14.7 psia) and a specified temperature (typically 100° C. (212°F.), or room temperature, that being about 23° C. (73° F.) at variousconcentrations in air in order to determine the lower flammability limit(LFL) and upper flammability limit (UFL) of the test compound in air.

In practical terms, a refrigerant may be classified as flammable if uponleaking from a refrigeration apparatus or air-conditioning apparatus,and contacting an ignition source a fire may result. The compositions ofthe present invention, during such a leak, have a low probability ofcausing a fire.

Flammable refrigerants of the present invention includehydrofluorocarbons (HFCs), fluoroolefins, fluoroethers, hydrocarbonethers, hydrocarbons, ammonia (NH₃), and combinations thereof.

Flammable HFC refrigerants include but are not limited to:difluoromethane (HFC-32), fluoromethane (HFC-41), 1,1,1-trifluoroethane(HFC-143a), 1,1,2-trifluoroethane (HFC-143), 1,1-difluoroethane(HFC-152a), fluoroethane (HFC-161), 1,1,1-trifluoropropane (HFC-263fb),1,1,1,3,3-pentafluoropropane (HFC-365mfc), and combinations thereof.These flammable HFC refrigerants are commercial products available froma number of sources such as chemical synthesis companies or may beprepared by synthetic processes disclosed in the art.

Flammable refrigerants of the present invention further comprisefluoroolefins including but not limited to:1,2,3,3-tetrafluoro-1-propene (HFC-1234ye);1,3,3,3-tetrafluoro-1-propene (HFC-1234ze);2,3,3,3-tetrafluoro-1-propene (HFC-1234yf);1,1,2,3-tetrafluoro-1-propene (HFC-1234yc);1,1,3,3-tetrafluoro-1-propene (HFC-1234zc); 2,3,3-trifluoro-1-propene(HFC-1243yf); 3,3,3-trifluoro-1-propene (HFC-1243zf);1,1,2-trifluoro-1-propene (HFC-1243yc); 1,1,3-trifluoro-1-propene(HFC-1243zc); 1,2,3-trifluoro-1-propene (HFC-1243ye); and1,3,3-trifluoro-1-propene (HFC-1243ze).

Flammable refrigerants of the present invention further comprisefluoroethers, compounds similar to hydrofluorocarbons, which alsocontain at least one ether group oxygen atom. Representative fluoroetherrefrigerants include but are not limited to C₄F₉OC₂H₅, availablecommercially.

Flammable refrigerants of the present invention further comprisehydrocarbon refrigerants. Representative hydrocarbon refrigerantsinclude but are not limited to propane, propylene, cyclopropane,n-butane, isobutane, n-pentane, 2-methylbutane (isopentane),cyclobutane, cyclopentane, 2,2-dimethylpropane, 2,2-dimethylbutane,2,3-dimethylbutane, 2,3-dimethylpentane, 2-methylhexane, 3-methylhexane,2-methylpentane, 3-ethylpentane, 3-methylpentane, cyclohexane,n-heptane, methylcyclopentane, and n-hexane. Flammable hydrocarbonrefrigerants are readily available from multiple commercial sources.

Flammable refrigerants of the present invention further comprisehydrocarbon ethers, such as dimethyl ether (DME, CH3OCH3) and methylt-butyl ether (MTBE, (CH3)3COCH3), both available from multiplecommercial sources.

Flammable refrigerants of the present invention further comprise ammonia(NH3), a commercially available compound.

Flammable refrigerants of the present invention may further comprisemixtures of more than one refrigerant such as a mixture of two or moreflammable refrigerants (eg. two HFCs or an HFC and a hydrocarbon) or amixture comprising a flammable refrigerant and a non-flammablerefrigerant, such that the overall mixture is still considered to be aflammable refrigerant, identified under the ASTM conditions describedherein, or in practical terms.

Examples of non-flammable refrigerants that may be combined with otherrefrigerants of the present invention include R-134a, R-134, R-23, R125,R-236fa, R-245fa, and mixtures of HCFC-22/HFC-152a/HCFC-124 (known bythe ASHRAE designations, R401 or R-401A, R-401B, and R-401C),HFC-125/HFC-143a/HFC-134a (known by the ASHRAE designation, R-404 orR-404A), HFC-32/HFC-125/HFC-134a (known by ASHRAE designations, R407 orR-407A, R-407B, and R-407C), HCFC-22/HFC-143a/HFC-125 (known by theASHRAE designation, R408 or R-408A), HCFC-22/HCFC-124/HCFC-142b (knownby the ASHRAE designation: R-409 or R-409A), HFC-32/HFC-125 (known bythe ASHRAE designation R-410A), and HFC-125/HFC-143a (known by theASHRAE designation: R-507 or R507A) and carbon dioxide.

Examples of mixtures of more than one flammable refrigerant includepropane/isobutane; HFC-152a/isobutane, R32/propane; R32/isobutane; andHFC/carbon dioxide mixtures such as HFC-152a/CO₂.

One aspect of the present invention is to provide a non-flammablerefrigerant with a global warming potential of less than 150, preferablyless than 50. Another aspect of the present invention is to reduce theflammability of flammable refrigeration mixtures by adding non-flammablefluoroolefins to said mixtures.

It may be demonstrated that while certain refrigerants are flammable, itis possible to produce a non-flammable refrigerant composition by addingto the flammable refrigerant another compound that is not flammable.Examples of such nonflammable refrigerant blends include R-410A (HFC-32is a flammable refrigerant, while HFC-125 is non-flammable), and R-407C(HFC-32 is a flammable refrigerant, while HFC-125 and HFC-134a are notflammable).

The compositions of the present invention that are useful asrefrigerants or heat transfer fluids comprising at least onefluoroolefin and at least one flammable refrigerant may contain aneffective amount of fluoroolefin to produce a composition that isnon-flammable based upon results of ASTM E681-01.

The present inventive compositions comprising at least one flammablerefrigerant and at least one fluoroolefin may contain about 1 weightpercent to about 99 weight percent fluoroolefin and about 99 weightpercent to about 1 weight percent flammable refrigerant.

In another embodiment, the compositions of the present invention maycontain about 10 weight percent to about 80 weight percent fluoroolefinand about 90 weight percent to about 20 weight percent flammablerefrigerant. In yet another embodiment, the compositions of the presentinvention may contain about 20 weight percent to about 70 weight percentfluoroolefin and about 80 weight percent to about 30 weight percentflammable refrigerant.

Of particular interest is an embodiment of the present disclosurewherein the fluoroolefin comprises HFC-1225ye and the flammablerefrigerant comprises HFC-32 (difluoromethane). It has been determinedthat compositions comprising up to 37 weight percent HFC-32 arenon-flammable, while compositions comprising 38 weight percent HFC-32 orgreater are flammable as determined by ASTM 681-01. The presentdisclosure provides non-flammable compositions comprising about 1.0weight percent to about 37.0 weight percent HFC-32 and about 99.0 weightpercent to about 63 weight percent HFC-1225ye.

Also, of particular interest is an embodiment of the present disclosurewherein the composition comprises HFC-1225ye, HFC-32 and HFC-125. Thiscomposition of the present invention comprises about 20 weight percentto about 95 weight percent HFC-1225ye, about 1.0 weight percent to about65 weight percent HFC-32, and about 1.0 weight percent to about 40weight percent HFC-125. In another embodiment, the composition comprisesabout 30 weight percent to about 90 weight percent HFC-1225ye, about 5.0weight percent to about 55 weight percent HFC-32, and about 1.0 weightpercent to about 35 weight percent HFC-125. In yet another embodiment,the composition comprises about 40 weight percent to about 85 weightpercent HFC-1225ye, about 10 weight percent to about 45 weight percentHFC-32 and about 1.0 weight percent to about 28 weight percent HFC-125.Those compositions containing less than about 40 weight percent HFC-32are expected to be non-flammable compositions. This flammability limitwill vary from less than about 45 weight percent HFC-32 to less thanabout 37 weight percent HFC-32 depending on the relative ratios ofHFC-1225ye and HFC-125 present in the composition.

In another embodiment of particular interest, the flammable refrigerantcomprises HFC-1243zf and a non-flammable fluoroolefin intended to reducethe flammability of the overall composition. The composition maycomprise about 1.0 weight percent to about 99 weight percent HFC-1243zfand about 99 weight percent to about 1.0 weight percent HFC-1225ye.Alternatively, the composition may comprise about 40 weight percent toabout 70 weight percent HFC-1243zf and about 60 weight percent to about30 weight percent HFC-1225ye.

In another embodiment of particular interest, the composition comprisesabout 1.0 weight percent to about 98 weight percent HFC-1243zf; about1.0 weight percent to about 98 weight percent HFC-1225ye; and about 1.0weight percent to about 50 weight percent HFC-125. Alternatively, thecomposition comprises about 40 weight percent to about 70 weight percentHFC-1243zf; about 20 weight percent to about 60 weight percentHFC-1225ye; and about 1.0 weight percent to about 10 weight percentHFC-125.

In another embodiment of particular interest the composition comprisesabout 1.0 weight percent to about 98 weight percent HFC-1243zf; about1.0 weight percent to about 98 weight percent HFC-1225ye; and about 1.0weight percent to about 50 weight percent HFC-32. Alternatively, thecomposition comprises about 40 weight percent to about 70 weight percentHFC-1243zf; about 20 weight percent to about 60 weight percentHFC-1225ye; and about 1.0 weight percent to about 10 weight percentHFC-32.

In yet another embodiment of particular interest, the compositioncomprises about 1.0 weight percent to about 97 weight percentHFC-1243zf; about 1.0 weight percent to about 97 weight percentHFC-1225ye; about 1.0 weight percent to about 50 weight percent HFC-125;and about 1.0 weight percent to about 50 weight percent HFC-32.

Alternatively, the composition comprises about 40 weight percent toabout 70 weight percent HFC-1243zf; about 20 weight percent to about 60weight percent HFC-1225ye; and about 1.0 weight percent to about 10weight percent HFC-125; and about 1.0 weight percent to about 10 weightpercent HFC-32.

The present invention further relates to a method for reducing theflammability of a flammable refrigerant said method comprising combiningthe flammable refrigerant with at least one fluoroolefin. The amount offluoroolefin added must be an effective amount to produce anon-flammable compositions as determined by ASTM 681-01.

Compositions of the present invention may be used in combination with adesiccant in a refrigeration, air-conditioning, or heat pump system toaid in removal of moisture. Desiccants may be composed of activatedalumina, silica gel, or zeolite based molecular sieves. Representativemolecular sieves include MOLSIV XH-7, XH-6, XH-9 and XH-11 (UOP LLC, DesPlaines, Ill.). For refrigerants with small molecular size such asHFC-32, XH-11 desiccant is preferred.

The compositions of the present invention may further comprise at leastone lubricant. Lubricants of the present invention comprise thosesuitable for use with refrigeration or air-conditioning apparatus. Amongthese lubricants are those conventionally used in compressionrefrigeration apparatus utilizing chlorofluorocarbon refrigerants. Suchlubricants and their properties are discussed in the 1990 ASHRAEHandbook, Refrigeration Systems and Applications, chapter 8, titled“Lubricants in Refrigeration Systems”, pages 8.1 through 8.21, hereinincorporated by reference. Lubricants of the present invention maycomprise those commonly known as “mineral oils” in the field ofcompression refrigeration lubrication. Mineral oils comprise paraffins(i.e. straight-chain and branched-carbon-chain, saturated hydrocarbons),naphthenes (i.e. cyclic paraffins) and aromatics (i.e. unsaturated,cyclic hydrocarbons containing one or more rings characterized byalternating double bonds). Lubricants of the present invention furthercomprise those commonly known as “synthetic oils” in the field ofcompression refrigeration lubrication. Synthetic oils comprisealkylaryls (i.e. linear and branched alkyl alkylbenzenes), syntheticparaffins and naphthenes, and poly(alphaolefins). Representativeconventional lubricants of the present invention are the commerciallyavailable BVM 100 N (paraffinic mineral oil sold by BVA Oils), Suniso®3GS and Suniso® 5GS (naphthenic mineral oil sold by Crompton Co.),Sontex® 372LT (naphthenic mineral oil sold by Pennzoil), Calumet® RO-30(naphthenic mineral oil sold by Calumet Lubricants), Zerol® 75, Zerol®150 and Zerol® 500 (linear alkylbenzenes sold by Shrieve Chemicals) andHAB 22 (branched alkylbenzene sold by Nippon Oil).

Lubricants of the present invention further comprise those, which havebeen designed for use with hydrofluorocarbon refrigerants and aremiscible with refrigerants of the present invention under compressionrefrigeration and air-conditioning apparatus' operating conditions. Suchlubricants and their properties are discussed in “Synthetic Lubricantsand High-Performance Fluids”, R. L. Shubkin, editor, Marcel Dekker,1993. Such lubricants include, but are not limited to, polyol esters(POEs) such as Castrol® 100 (Castrol, United Kingdom), polyalkyleneglycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Mich.),and polyvinyl ethers (PVEs).

Lubricants of the present invention are selected by considering a givencompressor's requirements and the environment to which the lubricantwill be exposed.

Commonly used refrigeration system additives may optionally be added, asdesired, to compositions of the present invention in order to enhancelubricity and system stability. These additives are generally knownwithin the field of refrigeration compressor lubrication, and includeanti wear agents, extreme pressure lubricants, corrosion and oxidationinhibitors, metal surface deactivators, foaming and antifoam controlagents, leak detectants and the like. In general, these additives arepresent only in small amounts relative to the overall lubricantcomposition. They are typically used at concentrations of from less thanabout 0.1% to as much as about 3% of each additive. These additives areselected on the basis of the individual system requirements. Sometypical examples of such additives may include, but are not limited to,lubrication enhancing additives, such as alkyl or aryl esters ofphosphoric acid and of thiophosphates. Additionally, the metal dialkyldithiophosphates (e.g. zinc dialkyl dithiophosphate or ZDDP, Lubrizol1375) and other members of this family of chemicals may be used incompositions of the present invention. Other antiwear additives includenatural product oils and assymetrical polyhydroxyl lubrication additivessuch as Synergol TMS (International Lubricants). Similarly, stabilizerssuch as antioxidants, free radical scavengers, and water scavengers(drying compounds) may be employed. Such additives include but are notlimited to, nitromethane, hindered phenols (such as butylated hydroxytoluene, or BHT), hydroxylamines, thiols, phosphites, epoxides orlactones. Water scavengers include but are not limited to ortho esterssuch as trimethyl-, triethyl-, or tripropylortho formate. Singleadditives or combinations may be used.

In one embodiment, the present invention provides compositionscomprising at least one fluoroolefin and at least one stabilizerselected from the group consisting of thiophosphates, butylatedtriphenylphosphorothionates, organo phosphates, dialkylthiophosphateesters, terpenes, terpenoids, fullerenes, functionalizedperfluoropolyethers, polyoxyalkylated aromatics, epoxides, fluorinatedepoxides, oxetanes, ascorbic acid, thiols, lactones, thioethers,nitromethanes, alkylsilanes, benzophenone derivatives, arylsulfide,divinyl terephthalate, diphenyl terephthalate, alkylamines, hinderedamine antioxidants, and phenols, The alkylamines can includetriethylamine, tributylamine, diisopropylamine, triisopropylamine,triisobutylamine, and other members of this family of alkylaminecompounds.

In another embodiment, the stabilizers of the present invention maycomprise specific combinations of stabilizers. One combination ofstabilizers of particular interest comprises at least one terpene orterpenoid. These terpenes or terpenoids may be combined with at leastone compound selected from epoxides, fluorinated epoxides, and oxetanes.

Terpenes are hydrocarbon compounds characterized by structurescontaining more than one repeating isoprene (2-methyl-1,3-butadiene)unit. Terpenes may be acyclic or cyclic. Representative terpenes includebut are not limited to myrcene (2-methyl-6-methyl-eneocta-1,7-diene),allo-cimene, beta-ocimene, terebene, limonene (or d-limonene), retinal,pinene (or alpha-pinene), menthol, geraniol, farnesol, phytol, VitaminA, terpinene, delta-3-carene, terpinolene, phellandrene, fenchene andmixtures thereof. Terpene stabilizers are commercially available or maybe prepared by methods known in the art or isolated from naturalsources.

Terpenoids are natural products and related compounds characterized bystructures containing more than one repeating isoprene unit andoptionally contain oxygen. Representative terpenoids includecarotenoids, such as lycopene (CAS reg. no. [502-65-8]), betacarotene(CAS reg. no. [7235-40-7]), and xanthophylls, i.e. zeaxanthin (CAS reg.no. [144-68-3]); retinoids, such as hepaxanthin (CAS reg. no.[512-39-0]), and isotretinoin (CAS reg. no. [4759-48-2]); abietane (CASreg. no. [640-43-7]); ambrosane (CAS reg. no. [24749-18-6]); aristolane(CAS reg. no. [29788-49-6]); atisane (CAS reg. no. [24379-83-7]);beyerane (CAS reg. no. [2359-83-3]), bisabolane (CAS reg. no.[29799-19-7]); bornane (CAS reg. no. [464-15-3]); caryophyllane (CASreg. no. [20479-00-9]); cedrane (CAS reg. no. [13567-54-9]); dammarane(CAS reg. no. [545-22-2]); drimane (CAS reg. no. [5951-58-6]);eremophilane (CAS reg. no. [3242-05-5]); eudesmane (CAS reg. no.[473-11-0]); fenchane (CAS reg. no. [6248-88-0]); gammacerane (CAS reg.no. [559-65-9]); germacrane (CAS reg. no. [645-10-3]); gibbane (CAS reg.no. [6902-95-0]); grayanotoxane (CAS reg. no. [39907-73-8]); guaiane(CAS reg. no. [489-80-5]); himachalane (CAS reg. no. [20479-45-2]);hopane (CAS reg. no. [471-62-5]); humulane (CAS reg. no. [430-19-3]);kaurane (CAS reg. no. [1573-40-6]); labdane (CAS reg. no. [561-90-0]);lanostane (CAS reg. no. [474-20-4]); lupane (CAS reg. no. [464-99-3]);p-menthane (CAS reg. no. [99-82-1]); oleanane (CAS reg. no. [471-67-0]);ophiobolane (CAS reg. no. [20098-65-1]); picrasane (CAS reg. no.[35732-97-9]); pimarane (CAS reg. no. [30257-03-5]); pinane (CAS reg.no. [473-55-2]); podocarpane (CAS reg. no. [471-78-3]); protostane (CASreg. no. [70050-78-1]); rosane (CAS reg. no. [6812-82-4]); taxane (CASreg. no. [1605-68-1]); thujane (CAS reg. no. [471-12-5]); trichothecane(CAS reg. no. [24706-08-9]); and ursane (CAS reg. no. [464-93-7]). Theterpenoids of the present invention are commercially available or may beprepared by methods known in the art or may be isolated from thenaturally occurring source.

In one embodiment, the terpene or terpenoid stabilizers may be combinedwith at least one epoxide. Representative epoxides include 1,2-propyleneoxide (CAS reg. no. [75-56-9]); 1,2-butylene oxide (CAS reg. no.[106-88-7]); or mixtures thereof.

In another embodiment, the terpene or terpenoid stabilizers of thepresent invention may be combined with at least one fluorinated epoxide.The fluorinated epoxides of the present invention may be depicted byFormula 3, wherein each of R² through R⁵ is H, alkyl of 1-6 carbon atomsor fluoroalkyl of 1-6 carbon atoms with the proviso that at least one ofR² through R⁵ is a fluoroalkyl group.

Representative fluorinated epoxide stabilizers include but are notlimited to trifluoromethyloxirane and 1,1-bis(trifluoromethyl)oxirane.Such compounds may be prepared by methods known in the art, for instanceby methods described in, Journal of Fluorine Chemistry, volume 24, pages93-104 (1984), Journal of Organic Chemistry, volume 56, pages 3187 to3189 (1991), and Journal of Fluorine Chemistry, volume 125, pages 99-105(2004).

In another embodiment, the terpene or terpenoid stabilizers of thepresent invention may be combined with at least one oxetane. The oxetanestabilizers of the present invention may be compounds with one or moreoxetane groups and is represented by Formula 4, wherein R₁-R₆ are thesame or different and can be selected from hydrogen, alkyl orsubstituted alkyl, aryl or substituted aryl.

Representative oxetane stabilizers include but are not limited to3-ethyl-3-hydroxymethyl-oxetane, such as OXT-101 (Toagosei Co., Ltd);3-ethyl-3-((phenoxy)methyl)-oxetane, such as OXT-211 (Toagosei Co.,Ltd); and 3-ethyl-3-((2-ethyl-hexyloxy)methyl)-oxetane, such as OXT-212(Toagosei Co., Ltd).

Another embodiment of particular interest is a combination ofstabilizers comprising fullerenes. The fullerene stabilizers may becombined with at least one compound selected from the group consistingof epoxides, fluorinated epoxides, and oxetanes. The epoxides,fluorinated epoxides, and oxetanes for combination with fullerenes havebeen previously described herein as for combination with terpenes orterpenoids.

Another embodiment of particular interest is a combination ofstabilizers comprising phenols. The fullerene stabilizers may becombined with at least one compound selected from the group consistingof epoxides, fluorinated epoxides, and oxetanes. The epoxides,fluorinated epoxides, and oxetanes for combination with phenols havebeen previously described herein as for combination with terpenes orterpenoids.

Phenol stabilizers comprise any substituted or unsubstituted phenolcompound including phenols comprising one or more substituted orunsubstituted cyclic, straight chain, or branched aliphatic substituentgroup, such as, alkylated monophenols including2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-ethylphenol;2,4-dimethyl-6-tertbutylphenol; tocopherol; and the like, hydroquinoneand alkylated hydroquinones including t-butyl hydroquinone, otherderivatives of hydroquinone; and the like, hydroxylated thiodiphenylethers, including 4,4′-thio-bis(2-methyl-6-tert-butylphenol);4,4′-thiobis(3-methyl-6-tertbutylphenol);2,2′-thiobis(4methyl-6-tert-butylphenol); and the like,alkylidene-bisphenols including:4,4′-methylenebis(2,6-di-tert-butylphenol);4,4′-bis(2,6-di-tert-butylphenol); derivatives of 2,2′- or4,4-biphenoldiols; 2,2′-methylenebis(4-ethyl-6-tertbutylphenol);2,2′-methylenebis(4-methyl-6-tertbutylphenol);4,4-butylidenebis(3-methyl-6-tert-butylphenol);4,4-isopropylidenebis(2,6-di-tert-butylphenol);2,2′-methylenebis(4-methyl-6-nonylphenol);2,2′-isobutylidenebis(4,6-dimethylphenol;2,2′-methylenebis(4-methyl-6-cyclohexylphenol, 2,2- or 4,4-biphenyldiolsincluding 2,2′-methylenebis(4-ethyl-6-tert-butylphenol); butylatedhydroxyl toluene (BHT), bisphenols comprising heteroatoms including2,6-di-tert-alpha-dimethylamino-p-cresol,4,4-thiobis(6-tert-butyl-m-cresol); and the like; acylaminophenols;2,6-di-tert-butyl-4(N,N′-dimethylaminomethylphenol); sulfides including;bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide;bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; and the like.

In one embodiment of the present invention, these combinations ofstabilizers comprising terpenes or terpenoids, or fullerenes or phenolswith at least one compound selected from the group consisting ofepoxides, fluorinated epoxides, and oxetanes, may further comprise anadditional stabilizer compound selected from the group consisting of:

-   -   areoxalyl bis(benzylidene)hydrazide (CAS reg. no. 6629-10-3);    -   N,N′-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine)        (CAS reg. no. 32687-78-8);    -   2,2′-oxamidobis-ethyl-(3,5-d-tert-butyl-4-hydroxyhydrocinnamate)        (CAS reg. no. 70331-94-1);    -   N,N′-(disalicyclidene)-1,2-propanediamine (CAS reg. no.        94-91-1); and    -   ethyenediaminetetraacetic acid (CAS reg. no. 60-00-4) and salts        thereof.

In another embodiment of the present invention, these combinations ofstabilizers comprising terpenes or terpenoids, or fullerenes or phenolswith at least one compound selected from the group consisting ofepoxides, fluorinated epoxides, and oxetanes, may further comprise atleast one alkylamine selected from the group consisting oftriethylamine; tributylamine; triisopropylamine; diisobutylamine;triisopropylamine; triisobutylamine; and hindered amine antioxidants.

The compositions of the present invention may further comprise acompound or composition that is a tracer and is selected from the groupconsisting of hydrofluorocarbon (HFCs), deuterated hydrocarbon,deuterated hydrofluorocarbon, perfluorocarbons, fluoroether, brominatedcompound, iodated compound, alcohol, aldehyde, ketones, nitrous oxide(N₂O) and combinations thereof. The tracer used in the present inventionare different compositions from those used as refrigerant or heattransfer fluids, are added to the refrigerant and heat transfercompositions in previously determined quantities to allow detection ofany dilution, contamination or other alteration of the composition, asdescribed in U.S. patent application Ser. No. 11/062,044, filed Feb. 18,2005.

Typical tracer compounds for use in the present compositions are listedin Table 5.

TABLE 5 Compound Structure Deuterated hydrocarbons andhydrofluorocarbons Ethane-d6 CD₃CD₃ Propane-d8 CD₃CD₂CD₃ HFC-32-d2 CD₂F₂HFC-134a-d2 CD₂FCF₃ HFC-143a-d3 CD₃CF₃ HFC-125-d CDF₂CF₃ HFC-227ea-dCF₃CDFCF₃ HFC-227ca-d CF₃CF₂CDF₂ HFC-134-d2 CDF₂CDF₂ HFC-236fa-d2CF₃CD₂CF₃ HFC-245cb-d3 CF₃CF₂CD₃ HFC-263fb-d2* CF₃CD₂CH₃ HFC-263fb-d3CF₂CH₂CD₃ Fluoroethers HFOC-125E CHF₂OCF₃ HFOC-134aE CH₂FOCF₃ HFOC-143aECH₃OCF₃ HFOC-227eaE CF₃OCHF—F₃ HFOC-236faE CF₃OCH₂CF₃ HFOC-245faEβγ orHFOC-245faEαβ CHF₂OCH₂CF₃ (or CHF₂CH₂OCF₃) HFOC-245cbEβγ or HFOC-245cbαβCH₃OCF₂CF₃ (or CH₃CF₂OCF₃) HFE-42-11mcc (or Freon ® E1) CF₃CF₂CF₂OCHFCF₃Freon ® E2 CF₃CF₂CF₂OCF(CF₃)CF₂OCHFCF₃ Hydrofluorocarbons HFC-23 CHF₃HFC-161 CH₃CH₂F HFC-152a CH₃CHF₂ HFC-134 CHF₂CHF₂ HFC-227ea CF₃CHFCF₃HFC-227ca CHF₂CF₂CF₃ HFC-236cb CH₂FCF₂CF₃ HFC-236ea CF₃CHFCHF₂ HFC-236faCF₃CH₂CF₃ HFC-245cb CF₃CF₂CH₃ HFC-245fa CHF₂CH₂CF₃ HFC-254cb CHF₂CF₂CH₃HFC-254eb CF₃CHFCH₃ HFC-263fb CF₃CH₂CH₃ HFC-272ca CH₃CF₂CH₃ HFC-281eaCH₃CHFCH₃ HFC-281fa CH₂FCH₂CH₃ HFC-329p CHF₂CF₂CF₂CF₃ HFC-329mmz(CH₃)₂CHCF₃ HFC-338mf CF₃CH₂CF₂CF₃ HFC-338pcc CHF₂CF₂CF₂CHF₂ HFC-347sCH₃CF₂CF₂CF₃ HFC-43-10mee CF₃CHFCHFCF₂CF₃ Perfluorocarbons PFC-116CF₃CF₃ PFC-C216 Cyclo(—CF₂CF₂CF₂—) PFC-218 CF₃CF₂CF₃ PFC-C318Cyclo(—CF₂CF₂CF₂CF₂—) PFC-31-10mc CF₃CF₂CF₂CF₃ PFC-31-10my (CF₃)₂CFCF₃PFC-C51-12mycm Cyclo(—CF(CF₃)CF₂CF(CF₃)CF₂—) PFC-C51-12mym, transCyclo(—CF₂CF(CF₃)CF(CF₃CF₂—) PFC-C51-12mym, cisCyclo(—CF₂CF(CF₃)CF(CF₃)CF₂—) Perfluoromethylcyclo-pentaneCyclo(—CF₂CF₂(CF₃)CF₂CF₂CF₂—) Perfluoromethylcyclo-hexaneCyclo(—CF₂CF₂(CF₃)CF₂CF₂CF₂CF₂—) Perfluorodimethylcyclo-hexane (ortho,meta, or para) Cyclo(—CF₂CF₂(CF₃)CF₂CF₂(CF₃)CF₂—)Perfluoroethylcyclohexane Cyclo(—CF₂CF₂(CF₂CF₃)CF₂CF₂CF₂CF₂—)Perfluoroindan C₉F₁₀ (see structure below)

Perfluorotrimethylcyclo-hexane (all possible isomers)Cyclo(—CF₂(CF₃)CF₂(CF₃)CF₂CF₂(CF₃)CF₂—) Perfluoroisopropylcyclo-hexaneCyclo(—CF₂CF₂(CF₂(CF₃)₂)CF₂CF₂CF₂CF₂—) Perfluorodecalin (cis or trans,trans shown) C₁₀F₁₈ (see structure below)

Perfluoromethyldecalin (cis or trans C₁₁F₂₀ (see structure below) andall additional possible isomers)

Brominated compounds Bromomethane CH₃Br Bromofluoromethane CH₂FBrBromodifluoromethane CHF₂Br Dibromofluoromethane CHFBr₂ TribromomethaneCHBr₃ Bromoethane CH₃CH₂Br Bromoethene CH₂═CHBr 1,2-dibromoethaneCH₂BrCH₂Br 1-bromo-1,2-difluoroethene CFBr═CHF Iodated compoundsIodotrifluoromethane CF₃I Difluoroiodomethane CHF₂I FluoroiodomethaneCH₂FI 1,1,2-trifluoro-1-iodoethane CF₂ICH₂F1,1,2,2-tetrafluoro-1-iodoethane CF₂ICHF₂1,1,2,2-tetrafluoro-1,2-diiodoethane CF₂ICF₂I IodopentafluorobenzeneC₆F₅I Alcohols Ethanol CH₃CH₂OH n-propanol CH₃CH₂CH₂OH IsopropanolCH₃CH(OH)CH₃ Aldehydes and Ketones Acetone (2-propanone) CH₃C(O)CH₃n-propanal CH₃CH₂CHO n-butanal CH₃CH₂CH₂CHO Methyl ethyl ketone(2-butanone) CH₃C(O)CH₂CH₃ Other Nitrous oxide N₂O

The compounds listed in Table 5 are available commercially (fromchemical supply houses) or may be prepared by processes known in theart.

Single tracer compounds may be used in combination with arefrigeration/heating fluid in the compositions of the present inventionor multiple tracer compounds may be combined in any proportion to serveas a tracer blend. The tracer blend may contain multiple tracercompounds from the same class of compounds or multiple tracer compoundsfrom different classes of compounds. For example, a tracer blend maycontain 2 or more deuterated hydrofluorocarbons, or one deuteratedhydrofluorocarbon in combination with one or more perfluorocarbons.

Additionally, some of the compounds in Table 4 exist as multipleisomers, structural or optical. Single isomers or multiple isomers ofthe same compound may be used in any proportion to prepare the tracercompound. Further, single or multiple isomers of a given compound may becombined in any proportion with any number of other compounds to serveas a tracer blend.

The tracer compound or tracer blend may be present in the compositionsat a total concentration of about 50 parts per million by weight (ppm)to about 1000 ppm. Preferably, the tracer compound or tracer blend ispresent at a total concentration of about 50 ppm to about 500 ppm andmost preferably, the tracer compound or tracer blend is present at atotal concentration of about 100 ppm to about 300 ppm.

The compositions of the present invention may further comprise anultra-violet (UV) dye and optionally a solubilizing agent. The UV dye isa useful component for detecting leaks of the refrigerant composition orheat transfer fluids by permitting one to observe the fluorescence ofthe dye in the refrigerant or heat transfer fluid composition at or inthe vicinity of a leak point in said apparatus in the refrigeration,air-conditioning, heat pump apparatus. One may observe the fluorescenceof the dye under an ultra-violet light. Solubilizing agents may beneeded due to poor solubility of such UV dyes in some refrigerants andheat transfer fluids.

By “ultra-violet” dye is meant a UV fluorescent composition that absorbslight in the ultra-violet or “near” ultra-violet region of theelectromagnetic spectrum. The fluorescence produced by the UVfluorescent dye under illumination by a UV light that emits radiationwith wavelength anywhere from 10 nanometer to 750 nanometer may bedetected. Therefore, if refrigerant or heat transfer fluid containingsuch a UV fluorescent dye is leaking from a given point in arefrigeration, air-conditioning, or heat pump apparatus, thefluorescence can be detected at the leak point, or in the vicinity ofthe leak point. Such UV fluorescent dyes include but are not limited tonaphthalimides, perylenes, coumarins, anthracenes, phenanthracenes,xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, andderivatives of said dye or combinations thereof. Solubilizing agents ofthe present invention comprise at least one compound selected from thegroup consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkyleneglycol ethers, amides, nitriles, ketones, chlorocarbons, esters,lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes.

Hydrocarbon solubilizing agents of the present invention comprisehydrocarbons including straight chained, branched chain or cyclicalkanes or alkenes containing 16 or fewer carbon atoms and only hydrogenwith no other functional groups. Representative hydrocarbon solubilizingagents comprise propane, propylene, cyclopropane, n-butane, isobutane,n-pentane, octane, decane, and hexadecane. It should be noted that ifthe refrigerant is a hydrocarbon, then the solubilizing agent may not bethe same hydrocarbon.

Hydrocarbon ether solubilizing agents of the present invention compriseethers containing only carbon, hydrogen and oxygen, such as dimethylether (DME).

Polyoxyalkylene glycol ether solubilizing agents of the presentinvention are represented by the formula R¹[(OR²)_(x)OR³]_(y), wherein:x is an integer from 1-3; y is an integer from 1-4; R¹ is selected fromhydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atomsand y bonding sites; R² is selected from aliphatic hydrocarbyleneradicals having from 2 to 4 carbon atoms; R³ is selected from hydrogenand aliphatic and alicyclic hydrocarbon radicals having from 1 to 6carbon atoms; at least one of R¹ and R³ is said hydrocarbon radical; andwherein said polyoxyalkylene glycol ethers have a molecular weight offrom about 100 to about 300 atomic mass units. As used herein, bondingsites mean radical sites available to form covalent bonds with otherradicals. Hydrocarbylene radicals mean divalent hydrocarbon radicals. Inthe present invention, preferred polyoxyalkylene glycol ethersolubilizing agents are represented by R¹[(OR²)_(x)OR³]_(y): x ispreferably 1-2; y is preferably 1; R¹ and R³ are preferablyindependently selected from hydrogen and aliphatic hydrocarbon radicalshaving 1 to 4 carbon atoms; R² is preferably selected from aliphatichydrocarbylene radicals having from 2 or 3 carbon atoms, most preferably3 carbon atoms; the polyoxyalkylene glycol ether molecular weight ispreferably from about 100 to about 250 atomic mass units, mostpreferably from about 125 to about 250 atomic mass units. The R¹ and R³hydrocarbon radicals having 1 to 6 carbon atoms may be linear, branchedor cyclic. Representative R¹ and R³ hydrocarbon radicals include methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, and cyclohexyl.Where free hydroxyl radicals on the present polyoxyalkylene glycol ethersolubilizing agents may be incompatible with certain compressionrefrigeration apparatus materials of construction (e.g. Mylar®), R¹ andR³ are preferably aliphatic hydrocarbon radicals having 1 to 4 carbonatoms, most preferably 1 carbon atom. The R² aliphatic hydrocarbyleneradicals having from 2 to 4 carbon atoms form repeating oxyalkyleneradicals —(OR²)_(x)— that include oxyethylene radicals, oxypropyleneradicals, and oxybutylene radicals. The oxyalkylene radical comprisingR² in one polyoxyalkylene glycol ether solubilizing agent molecule maybe the same, or one molecule may contain different R² oxyalkylenegroups. The present polyoxyalkylene glycol ether solubilizing agentspreferably comprise at least one oxypropylene radical. Where R¹ is analiphatic or alicyclic hydrocarbon radical having 1 to 6 carbon atomsand y bonding sites, the radical may be linear, branched or cyclic.Representative R¹ aliphatic hydrocarbon radicals having two bondingsites include, for example, an ethylene radical, a propylene radical, abutylene radical, a pentylene radical, a hexylene radical, acyclopentylene radical and a cyclohexylene radical. Representative R¹aliphatic hydrocarbon radicals having three or four bonding sitesinclude residues derived from polyalcohols, such as trimethylolpropane,glycerin, pentaerythritol, 1,2,3-trihydroxycyclohexane and1,3,5-trihydroxycyclohexane, by removing their hydroxyl radicals.

Representative polyoxyalkylene glycol ether solubilizing agents includebut are not limited to: CH₃OCH₂CH(CH₃)O(H or CH₃) (propylene glycolmethyl (or dimethyl) ether), CH₃O[CH₂CH(CH₃)O]₂(H or CH₃) (dipropyleneglycol methyl (or dimethyl) ether), CH₃O[CH₂CH(CH₃)O]₃(H or CH₃)(tripropylene glycol methyl (or dimethyl) ether), C₂H₅OCH₂CH(CH₃)O(H orC₂H₅) (propylene glycol ethyl (or diethyl) ether), C₂H₅O[CH₂CH(CH₃)O]₂(Hor C₂H₅) (dipropylene glycol ethyl (or diethyl) ether),C₂H₅O[CH₂CH(CH₃)O]₃(H or C₂H₅) (tripropylene glycol ethyl (or diethyl)ether), C₃H₇OCH₂CH(CH₃)O(H or C₃H₇) (propylene glycol n-propyl (ordi-n-propyl) ether), C₃H₇O[CH₂CH(CH₃)O]₂(H or C₃H₇) (dipropylene glycoln-propyl (or di-n-propyl) ether), C₃H₇O[CH₂CH(CH₃)O]₃(H or C₃H₇)(tripropylene glycol n-propyl (or di-n-propyl) ether), C₄H₉OCH₂CH(CH₃)OH(propylene glycol n-butyl ether), C₄H₉O[CH₂CH(CH₃)O]₂(H or C₄H₉)(dipropylene glycol n-butyl (or di-n-butyl) ether),C₄H₉O[CH₂CH(CH₃)O]₃(H or C₄H₉) (tripropylene glycol n-butyl (ordi-n-butyl) ether), (CH₃)₃COCH₂CH(CH₃)OH (propylene glycol t-butylether), (CH₃)₃CO[CH₂CH(CH₃)O]₂(H or (CH₃)₃) (dipropylene glycol t-butyl(or di-t-butyl) ether), (CH₃)₃CO[CH₂CH(CH₃)O]₃(H or (CH₃)₃)(tripropylene glycol t-butyl (or di-t-butyl) ether), C₅H₁₁OCH₂CH(CH₃)OH(propylene glycol n-pentyl ether), C₄H₉OCH₂CH(C₂H₅)OH (butylene glycoln-butyl ether), C₄H₉O[CH₂CH(C₂H₅)O]₂H (dibutylene glycol n-butyl ether),trimethylolpropane tri-n-butyl ether (C₂H₅C(CH₂O(CH₂)₃CH₃)₃) andtrimethylolpropane di-n-butyl ether (C₂H₅C(CH₂OC(CH₂)₃CH₃)₂CH₂OH).

Amide solubilizing agents of the present invention comprise thoserepresented by the formulae R¹C(O)NR²R³ and cyclo-[R⁴C(O)N(R⁵)], whereinR¹, R², R³ and R⁵ are independently selected from aliphatic andalicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R⁴ isselected from aliphatic hydrocarbylene radicals having from 3 to 12carbon atoms; and wherein said amides have a molecular weight of fromabout 100 to about 300 atomic mass units. The molecular weight of saidamides is preferably from about 160 to about 250 atomic mass units. R¹,R², R³ and R⁵ may optionally include substituted hydrocarbon radicals,that is, radicals containing non-hydrocarbon substituents selected fromhalogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹,R², R³ and R⁵ may optionally include heteroatom-substituted hydrocarbonradicals, that is, radicals, which contain the atoms nitrogen (aza-),oxygen (oxa-) or sulfur (thia-) in a radical chain otherwise composed ofcarbon atoms. In general, no more than three non-hydrocarbonsubstituents and heteroatoms, and preferably no more than one, will bepresent for each 10 carbon atoms in R¹⁻³, and the presence of any suchnon-hydrocarbon substituents and heteroatoms must be considered inapplying the aforementioned molecular weight limitations. Preferredamide solubilizing agents consist of carbon, hydrogen, nitrogen andoxygen. Representative R¹, R², R³ and R⁵ aliphatic and alicyclichydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl,isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl,tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl and their configurational isomers. A preferredembodiment of amide solubilizing agents are those wherein R⁴ in theaforementioned formula cyclo-[R⁴C(O)N(R⁵)—] may be represented by thehydrocarbylene radical (CR⁶R⁷)_(n), in other words, the formula:cyclo-[(CR⁶R⁷)_(n)C(O)N(R⁵)—] wherein: the previously-stated values formolecular weight apply; n is an integer from 3 to 5; R⁵ is a saturatedhydrocarbon radical containing 1 to 12 carbon atoms; R⁶ and R⁷ areindependently selected (for each n) by the rules previously offereddefining R¹⁻³. In the lactams represented by the formula:cyclo-[(CR⁶R⁷)_(n)C(O)N(R⁵)—], all R⁶ and R⁷ are preferably hydrogen, orcontain a single saturated hydrocarbon radical among the n methyleneunits, and R⁵ is a saturated hydrocarbon radical containing 3 to 12carbon atoms. For example, 1-(saturated hydrocarbonradical)-5-methylpyrrolidin-2-ones.

Representative amide solubilizing agents include but are not limited to:1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one,1-octyl-5-methylpyrrolidin-2-one, 1-butylcaprolactam,1-cyclohexylpyrrolidin-2-one, 1-butyl-5-methylpiperid-2-one,1-pentyl-5-methylpiperid-2-one, 1-hexylcaprolactam,1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1-pentylpiperid-2-one,1,3-dimethylpiperid-2-one, 1-methylcaprolactam,1-butyl-pyrrolidin-2-one, 1,5-dimethylpiperid-2-one,1-decyl-5-methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one,N,N-dibutylformamide and N,N-diisopropylacetamide.

Ketone solubilizing agents of the present invention comprise ketonesrepresented by the formula R¹C(O)R², wherein R¹ and R² are independentlyselected from aliphatic, alicyclic and aryl hydrocarbon radicals havingfrom 1 to 12 carbon atoms, and wherein said ketones have a molecularweight of from about 70 to about 300 atomic mass units. R¹ and R² insaid ketones are preferably independently selected from aliphatic andalicyclic hydrocarbon radicals having 1 to 9 carbon atoms. The molecularweight of said ketones is preferably from about 100 to 200 atomic massunits. R¹ and R² may together form a hydrocarbylene radical connectedand forming a five, six, or seven-membered ring cyclic ketone, forexample, cyclopentanone, cyclohexanone, and cycloheptanone. R¹ and R²may optionally include substituted hydrocarbon radicals, that is,radicals containing non-hydrocarbon substituents selected from halogens(e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹ and R² mayoptionally include heteroatom-substituted hydrocarbon radicals, that is,radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-)or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.In general, no more than three non-hydrocarbon substituents andheteroatoms, and preferably no more than one, will be present for each10 carbon atoms in R¹ and R², and the presence of any suchnon-hydrocarbon substituents and heteroatoms must be considered inapplying the aforementioned molecular weight limitations. RepresentativeR¹ and R² aliphatic, alicyclic and aryl hydrocarbon radicals in thegeneral formula R¹C(O)R² include methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl,tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl and their configurational isomers, as well as phenyl,benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.

Representative ketone solubilizing agents include but are not limitedto: 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone,cyclohexanone, cycloheptanone, 2-heptanone, 3-heptanone,5-methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl ketone,4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4-decanone,2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone.

Nitrile solubilizing agents of the present invention comprise nitrilesrepresented by the formula R¹CN, wherein R¹ is selected from aliphatic,alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms,and wherein said nitriles have a molecular weight of from about 90 toabout 200 atomic mass units. R¹ in said nitrile solubilizing agents ispreferably selected from aliphatic and alicyclic hydrocarbon radicalshaving 8 to 10 carbon atoms. The molecular weight of said nitrilesolubilizing agents is preferably from about 120 to about 140 atomicmass units. R¹ may optionally include substituted hydrocarbon radicals,that is, radicals containing non-hydrocarbon substituents selected fromhalogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹ mayoptionally include heteroatom-substituted hydrocarbon radicals, that is,radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-)or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.In general, no more than three non-hydrocarbon substituents andheteroatoms, and preferably no more than one, will be present for each10 carbon atoms in R¹, and the presence of any such non-hydrocarbonsubstituents and heteroatoms must be considered in applying theaforementioned molecular weight limitations. Representative R¹aliphatic, alicyclic and aryl hydrocarbon radicals in the generalformula R¹CN include pentyl, isopentyl, neopentyl, tert-pentyl,cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyland their configurational isomers, as well as phenyl, benzyl, cumenyl,mesityl, tolyl, xylyl and phenethyl. Representative nitrile solubilizingagents include but are not limited to: 1-cyanopentane,2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1-cyanoheptane,1-cyanooctane, 2-cyanooctane, 1-cyanononane, 1-cyanodecane,2-cyanodecane, 1-cyanoundecane and 1-cyanododecane.

Chlorocarbon solubilizing agents of the present invention comprisechlorocarbons represented by the formula RCl_(x), wherein; x is selectedfrom the integers 1 or 2; R is selected from aliphatic and alicyclichydrocarbon radicals having 1 to 12 carbon atoms; and wherein saidchlorocarbons have a molecular weight of from about 100 to about 200atomic mass units. The molecular weight of said chlorocarbonsolubilizing agents is preferably from about 120 to 150 atomic massunits. Representative R aliphatic and alicyclic hydrocarbon radicals inthe general formula RCl_(x) include methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl,tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl and their configurational isomers.

Representative chlorocarbon solubilizing agents include but are notlimited to: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane,1-chlorohexane, 1,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane,1-chlorononane, 1-chlorodecane, and 1,1,1-trichlorodecane.

Ester solubilizing agents of the present invention comprise estersrepresented by the general formula R¹CO₂R², wherein R¹ and R² areindependently selected from linear and cyclic, saturated andunsaturated, alkyl and aryl radicals. Preferred esters consistessentially of the elements C, H and O, have a molecular weight of fromabout 80 to about 550 atomic mass units.

Representative esters include but are not limited to:

-   -   (CH₃)₂CHCH₂OOC(CH₂)₂₋₄OCOCH₂CH(CH₃)₂ (diisobutyl dibasic ester),        ethyl hexanoate, ethyl heptanoate, n-butyl propionate, n-propyl        propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid        ethoxyethyl ester, dipropyl carbonate, “Exxate 700” (a        commercial C₇ alkyl acetate), “Exxate 800” (a commercial C₈        alkyl acetate), dibutyl phthalate, and tert-butyl acetate.

Lactone solubilizing agents of the present invention comprise lactonesrepresented by structures [A], [B], and [C]:

These lactones contain the functional group —CO₂— in a ring of six (A),or preferably five atoms (B), wherein for structures [A] and [B], R₁through R₈ are independently selected from hydrogen or linear, branched,cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. EachR₁ through R₈ may be connected forming a ring with another R₁ throughR₈. The lactone may have an exocyclic alkylidene group as in structure[C], wherein R₁ through R₆ are independently selected from hydrogen orlinear, branched, cyclic, bicyclic, saturated and unsaturatedhydrocarbyl radicals. Each R₁ though R₆ may be connected forming a ringwith another R₁ through R₆. The lactone solubilizing agents have amolecular weight range of from about 80 to about 300 atomic mass units,preferred from about 80 to about 200 atomic mass units.

Representative lactone solubilizing agents include but are not limitedto the compounds listed in Table 6.

TABLE 6 Molecular Molecular Weight Additive Molecular Structure Formula(amu) (E,Z)-3-ethylidene-5-methyl- dihydro-furan-2-one

C₇H₁₀O₂ 126 (E,Z)-3-propylidene-5-methyl- dihydro-furan-2-one

C₈H₁₂O₂ 140 (E,Z)-3-butylidene-5-methyl- dihydro-furan-2-one

C₉H₁₄O₂ 154 (E,Z)-3-pentylidene-5-methyl- dihydro-furan-2-one

C₁₀H₁₆O₂ 168 (E,Z)-3-Hexylidene-5-methyl- dihydro-furan-2-one

C₁₁H₁₈O₂ 182 (E,Z)-3-Heptylidene-5-methyl- dihydro-furan-2-one

C₁₂H₂₀O₂ 196 (E,Z)-3-octylidene-5-methyl- dihydro-furan-2-one

C₁₃H₂₂O₂ 210 (E,Z)-3-nonylidene-5-methyl- dihydro-furan-2-one

C₁₄H₂₄O₂ 224 (E,Z)-3-(3,5,5- trimethylhexylidene)-5-methyl-dihydrofuran-2-one

C₁₄H₂₄O₂ 224 (E,Z)-3- cyclohexylmethylidene-5- methyl-dihydrofuran-2-one

C₁₂H₁₈O₂ 194 gamma-octalactone

C₈H₁₄O₂ 142 gamma-nonalactone

C₉H₁₆O₂ 156 gamma-decalactone

C₁₀H₁₈O₂ 170 gamma-undecalactone

C₁₁H₂₀O₂ 184 gamma-dodecalactone

C₁₂H₂₂O₂ 198 3-hexyldihydro-furan-2-one

C₁₀H₁₈O₂ 170 3-heptyldihydro-furan-2-one

C₁₁H₂₀O₂ 184 cis-3-ethyl-5-methyl-dihydro- furan-2-one

C₇H₁₂O₂ 128 cis-(3-propyl-5-methyl)- dihydro-furan-2-one

C₈H₁₄O₂ 142 cis-(3-butyl-5-methyl)-dihydro- furan-2-one

C₉H₁₆O₂ 156 cis-(3-pentyl-5-methyl)- dihydro-furan-2-one

C₁₀H₁₈O₂ 170 cis-3-hexyl-5-methyl-dihydro- furan-2-one

C₁₁H₂₀O₂ 184 cis-3-heptyl-5-methyl-dihydro- furan-2-one

C₁₂H₂₂O₂ 198 cis-3-octyl-5-methyl-dihydro- furan-2-one

C₁₃H₂₄O₂ 212 cis-3-(3,5,5-trimethylhexyl)-5- methyl-dihydro-furan-2-one

C₁₄H₂₆O₂ 226 cis-3-cyclohexylmethyl-5- methyl-dihydro-furan-2-one

C₁₂H₂₀O₂ 196 5-methyl-5-hexyl-dihydro- furan-2-one

C₁₁H₂₀O₂ 184 5-methyl-5-octyl-dihydro- furan-2-one

C₁₃H₂₄O₂ 212 Hexahydro-isobenzofuran-1- one

C₈H₁₂O₂ 140 delta-decalactone

C₁₀H₁₈O₂ 170 delta-undecalactone

C₁₁H₂₀O₂ 184 delta-dodecalactone

C₁₂H₂₂O₂ 198 mixture of 4-hexyl- dihydrofuran-2-one and 3-hexyl-dihydro-furan-2-one

C₁₀H₁₈O₂ 170

Lactone solubilizing agents generally have a kinematic viscosity of lessthan about 7 centistokes at 40° C. For instance, gamma-undecalactone haskinematic viscosity of 5.4 centistokes andcis-(3-hexyl-5-methyl)dihydrofuran-2-one has viscosity of 4.5centistokes both at 40° C. Lactone solubilizing agents may be availablecommercially or prepared by methods as described in U.S. patentapplication Ser. No. 10/910,495, filed Aug. 3, 2004, incorporated hereinby reference.

Aryl ether solubilizing agents of the present invention further comprisearyl ethers represented by the formula R¹OR², wherein: R¹ is selectedfrom aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R² isselected from aliphatic hydrocarbon radicals having from 1 to 4 carbonatoms; and wherein said aryl ethers have a molecular weight of fromabout 100 to about 150 atomic mass units. Representative R¹ arylradicals in the general formula R¹OR² include phenyl, biphenyl, cumenyl,mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R² aliphatichydrocarbon radicals in the general formula R¹OR² include methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.Representative aromatic ether solubilizing agents include but are notlimited to: methyl phenyl ether (anisole), 1,3-dimethyoxybenzene, ethylphenyl ether and butyl phenyl ether.

Fluoroether solubilizing agents of the present invention comprise thoserepresented by the general formula R¹OCF₂CF₂H, wherein R¹ is selectedfrom aliphatic, alicyclic, and aromatic hydrocarbon radicals having fromabout 5 to about 15 carbon atoms, preferably primary, linear, saturated,alkyl radicals. Representative fluoroether solubilizing agents includebut are not limited to: C₈H₁₇OCF₂CF₂H and C₆H₁₃OCF₂CF₂H. It should benoted that if the refrigerant is a fluoroether, then the solubilizingagent may not be the same fluoroether.

Fluoroether solubilizing agents may further comprise ethers derived fromfluoroolefins and polyols. The fluoroolefins may be of the type CF₂═CXY,wherein X is hydrogen, chlorine or fluorine, and Y is chlorine,fluorine, CF₃ or OR_(f), wherein R_(f) is CF₃, C₂F₅, or C₃F₇.Representative fluoroolefins are tetrafluoroethylene,chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethylvinylether. The polyols may be linear or branched. Linear polyols may be ofthe type HOCH₂(CHOH)_(x)(CRR′)_(y)CH₂OH, wherein R and R′ are hydrogen,or CH₃, or C₂H₅ and wherein x is an integer from 0-4, and y is aninteger from 0-4. Branched polyols may be of the typeC(OH)_(t)(R)_(u)(CH₂OH)_(v)[(CH₂)_(m)CH₂OH]_(w), wherein R may behydrogen, CH₃ or C₂H₅, m may be an integer from 0 to 3, t and u may be 0or 1, v and w are integers from 0 to 4, and also wherein t+u+v+w=4.Representative polyols are trimethylol propane, pentaerythritol,butanediol, and ethylene glycol.

1,1,1-Trifluoroalkane solubilizing agents of the present inventioncomprise 1,1,1-trifluoroalkanes represented by the general formulaCF₃R¹, wherein R¹ is selected from aliphatic and alicyclic hydrocarbonradicals having from about 5 to about 15 carbon atoms, preferablyprimary, linear, saturated, alkyl radicals. Representative1,1,1-trifluoroalkane solubilizing agents include but are not limitedto: 1,1,1-trifluorohexane and 1,1,1-trifluorododecane.

Solubilizing agents of the present invention may be present as a singlecompound, or may be present as a mixture of more than one solubilizingagent. Mixtures of solubilizing agents may contain two solubilizingagents from the same class of compounds, say two lactones, or twosolubilizing agents from two different classes, such as a lactone and apolyoxyalkylene glycol ether.

In the present compositions comprising refrigerant and UV fluorescentdye, or comprising heat transfer fluid and UV fluorescent dye, fromabout 0.001 weight percent to about 1.0 weight percent of thecomposition is UV dye, preferably from about 0.005 weight percent toabout 0.5 weight percent, and most preferably from 0.01 weight percentto about 0.25 weight percent.

Solubility of these UV fluorescent dyes in refrigerant and heat transfercompositions may be poor. Therefore, methods for introducing these dyesinto the refrigeration, air-conditioning, or heat pump apparatus havebeen awkward, costly and time consuming. U.S. Pat. No. RE 36,951,incorporated herein by reference, describes a method, which utilizes adye powder, solid pellet or slurry of dye that may be inserted into acomponent of the refrigeration or air-conditioning apparatus. Asrefrigerant and lubricant are circulated through the apparatus, the dyeis dissolved or dispersed and carried throughout the apparatus. Numerousother methods for introducing dye into a refrigeration orair-conditioning apparatus are described in the literature.

Ideally, the UV fluorescent dye could be dissolved in the refrigerantthereby not requiring any specialized method for introduction to therefrigeration, air-conditioning, or heat pump apparatus. The presentinvention relates to compositions including UV fluorescent dye, whichmay be introduced into the system dissolved in the refrigerant incombination with a solubilizing agent. The inventive compositions willallow the storage and transport of dye-containing refrigerant and heattransfer fluid even at low temperatures while maintaining the dye insolution.

In the present compositions comprising refrigerant, UV fluorescent dyeand solubilizing agent, or comprising heat transfer fluid and UVfluorescent dye and solubilizing agent, from about 1 to about 50 weightpercent, preferably from about 2 to about 25 weight percent, and mostpreferably from about 5 to about 15 weight percent of the combinedcomposition is solubilizing agent in the refrigerant or heat transferfluid. In the compositions of the present invention the UV fluorescentdye is present in a concentration from about 0.001 weight percent toabout 1.0 weight percent in the refrigerant or heat transfer fluid,preferably from 0.005 weight percent to about 0.5 weight percent, andmost preferably from 0.01 weight percent to about 0.25 weight percent.

Solubilizing agents such as ketones may have an objectionable odor,which can be masked by addition of an odor masking agent or fragrance.Typical examples of odor masking agents or fragrances may includeEvergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or OrangePeel, all of which are commercially available, as well as d-limonene andpinene. Such odor masking agents may be used at concentrations of fromabout 0.001% to as much as about 15% by weight based on the combinedweight of odor masking agent and solubilizing agent.

The present invention further relates to a method of using therefrigerant or heat transfer fluid compositions comprising ultravioletfluorescent dye to detect leaks in refrigeration apparatus,air-conditioning apparatus, or heat pump apparatus. The presence of thedye in the compositions allows for detection of leaking refrigerant inthe refrigeration, air-conditioning, or heat pump apparatus. Leakdetection helps to one to address, resolve and/or prevent inefficientoperation of the apparatus or system or equipment failure. Leakdetection also helps one contain chemicals used in the operation of theapparatus.

The method comprises providing the composition comprising refrigerant,ultra-violet fluorescent dye or comprising heat transfer fluid and UVfluorescent dye, as described herein, and optionally, a solubilizingagent as described herein, to refrigeration, air-conditioning, or heatpump apparatus and employing a suitable means for detecting the UVfluorescent dye-containing refrigerant. Suitable means for detecting thedye include, but are not limited to, ultra-violet lamps, often referredto as a “black light” or “blue light”. Such ultra-violet lamps arecommercially available from numerous sources specifically designed fordetecting UV fluorescent dye. Once the ultra-violet fluorescent dyecontaining composition has been introduced to the refrigeration,air-conditioning, or heat pump apparatus and has been allowed tocirculate throughout the system, a leak point or the vicinity of theleak point can be located by shining said ultra-violet lamp on theapparatus and observing the fluorescence of the dye in the vicinity ofany leak point.

Mechanical refrigeration is primarily an application of thermodynamicswherein a cooling medium, such as a refrigerant, goes through a cycle sothat it can be recovered for reuse. Commonly used cycles includevapor-compression, absorption, steam-jet or steam-ejector, and air.

Vapor-compression refrigeration systems include an evaporator, acompressor, a condenser, and an expansion device. A vapor-compressioncycle re-uses refrigerant in multiple steps producing a cooling effectin one step and a heating effect in a different step. The cycle can bedescribed simply as follows. Liquid refrigerant enters an evaporatorthrough an expansion device, and the liquid refrigerant boils in theevaporator at a low temperature to form a gas and produce cooling. Thelow-pressure gas enters a compressor where the gas is compressed toraise its pressure and temperature. The higher-pressure (compressed)gaseous refrigerant then enters the condenser in which the refrigerantcondenses and discharges its heat to the environment. The refrigerantreturns to the expansion device through which the liquid expands fromthe higher-pressure level in the condenser to the low-pressure level inthe evaporator, thus repeating the cycle.

There are various types of compressors that may be used in refrigerationapplications. Compressors can be generally classified as reciprocating,rotary, jet, centrifugal, scroll, screw or axial-flow, depending on themechanical means to compress the fluid, or as positive-displacement(e.g., reciprocating, scroll or screw) or dynamic (e.g., centrifugal orjet), depending on how the mechanical elements act on the fluid to becompressed.

The compositions of the present invention comprising fluoroolefins maybe useful in any of the compressor types mentioned above. The choice ofrefrigerant for any given compressor will depend on many factorsincluding for instance, boiling point and vapor pressure requirements.

Either positive displacement or dynamic compressors may be used in thepresent inventive processes. A centrifugal type compressor is onepreferred type of equipment for certain of the refrigerant compositionscomprising at least one fluoroolefin.

A centrifugal compressor uses rotating elements to accelerate therefrigerant radially, and typically includes an impeller and diffuserhoused in a casing. Centrifugal compressors usually take fluid in at animpeller eye, or central inlet of a circulating impeller, and accelerateit radially outward. Some static pressure rise occurs in the impeller,but most of the pressure rise occurs in the diffuser section of thecasing, where velocity is converted to static pressure. Eachimpeller-diffuser set is a stage of the compressor. Centrifugalcompressors are built with from 1 to 12 or more stages, depending on thefinal pressure desired and the volume of refrigerant to be handled.

The pressure ratio, or compression ratio, of a compressor is the ratioof absolute discharge pressure to the absolute inlet pressure. Pressuredelivered by a centrifugal compressor is practically constant over arelatively wide range of capacities.

Positive displacement compressors draw vapor into a chamber, and thechamber decreases in volume to compress the vapor. After beingcompressed, the vapor is forced from the chamber by further decreasingthe volume of the chamber to zero or nearly zero. A positivedisplacement compressor can build up a pressure, which is limited onlyby the volumetric efficiency and the strength of the parts to withstandthe pressure.

Unlike a positive displacement compressor, a centrifugal compressordepends entirely on the centrifugal force of the high-speed impeller tocompress the vapor passing through the impeller. There is no positivedisplacement, but rather what is called dynamic-compression.

The pressure a centrifugal compressor can develop depends on the tipspeed of the impeller. Tip speed is the speed of the impeller measuredat its tip and is related to the diameter of the impeller and itsrevolutions per minute. The capacity of the centrifugal compressor isdetermined by the size of the passages through the impeller. This makesthe size of the compressor more dependent on the pressure required thanthe capacity.

Because of its high-speed operation, a centrifugal compressor isfundamentally a high volume, low-pressure machine. A centrifugalcompressor works best with a low-pressure refrigerant, such astrichlorofluoromethane (CFC-11) or 1,2,2-trichlorotrifluoroethane(CFC-113). Some of the low pressure refrigerant fluids of the presentinvention may be suitable as drop-in replacements for CFC-113 inexisting centrifugal equipment.

Large centrifugal compressors typically operate at 3000 to 7000revolutions per minute (rpm). Small turbine centrifugal compressors(mini-centrifugal compressors) are designed for high speeds, from about40,000 to about 70,000 (rpm), and have small impeller sizes, typicallyless than 0.15 meters (about 6 inches).

A multi-stage impeller may be used in a centrifugal compressor toimprove compressor efficiency thus requiring less power in use. For atwo-stage system, in operation, the discharge of the first stageimpeller goes to the suction intake of a second impeller. Both impellersmay operate by use of a single shaft (or axle). Each stage can build upa compression ratio of about 4 to 1; that is, the absolute dischargepressure can be four times the absolute suction pressure. Severalexamples of two-stage centrifugal compressor systems, particularly forautomotive applications, are described in U.S. Pat. No. 5,065,990 andU.S. Pat. No. 5,363,674, both incorporated herein by reference.

The present disclosure further relates to a method for producing heatingor cooling in a refrigeration, air-conditioning, or heat pump apparatus,said method comprising introducing a refrigerant or heat transfer fluidcomposition into said apparatus having (a) a centrifugal compressor; (b)a multi-stage centrifugal compressor, or (c) a single slab/single passheat exchanger; wherein said refrigerant or heat transfer fluidcomposition comprises at least one fluoroolefin selected from the groupconsisting of:

-   -   (i) fluoroolefins of the formula E- or Z-R¹CH═CHR², wherein R¹        and R² are, independently, C₁ to C₆ perfluoroalkyl groups;    -   (ii) cyclic fluoroolefins of the formula        cyclo-[CX═CY(CZW)_(n)—], wherein X, Y, Z, and W, independently,        are H or F, and n is an integer from 2 to 5; or    -   (iii) fluoroolefins selected from the group consisting of:        -   1,2,3,3,3-pentafluoro-1-propene (CF₃CF═CHF);            1,1,3,3,3-pentafluoro-1-propene (CF₃CH═CF₂);            1,1,2,3,3-pentafluoro-1-propene (CHF₂CF═CF₂);            1,2,3,3-tetrafluoro-1-propene (CHF₂CF═CHF);            2,3,3,3-tetrafluoro-1-propene (CF₃CF═CH₂);            1,3,3,3-tetrafluoro-1-propene (CF₃CH═CHF);            1,1,2,3-tetrafluoro-1-propene (CH₂FCF═CF₂);            1,1,3,3-tetrafluoro-1-propene (CHF₂CH═CF₂);            2,3,3-trifluoro-1-propene (CHF₂CF═CH₂);            3,3,3-trifluoro-1-propene (CF₃CH═CH₂);            1,1,2-trifluoro-1-propene (CH₃CF═CF₂);            1,1,3-trifluoro-1-propene (CH₂FCH═CF₂);            1,2,3-trifluoro-1-propene (CH₂FCF═CHF);            1,3,3-trifluoro-1-propene (CHF₂CH═CHF);            1,1,1,2,3,4,4,4-octafluoro-2-butene(CF₃CF═CFCF₃);            1,1,2,3,3,4,4,4-octafluoro-1-butene (CF₃CF₂CF═CF₂);            1,1,1,2,4,4,4-heptafluoro-2-butene (CF₃CF═CHCF₃);            1,2,3,3,4,4,4-heptafluoro-1-butene (CHF═CFCF₂CF₃);            1,1,1,2,3,4,4-heptafluoro-2-butene (CHF₂CF═CFCF₃);            1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene            ((CF₃)₂C═CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene            (CF₂═CHCF₂CF₃); 1,1,2,3,4,4,4-heptafluoro-1-butene            (CF₂═CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1-butene            (CF₂═CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1-butene            (CF₃CF₂CF═CH₂); 1,3,3,4,4,4-hexafluoro-1-butene            (CHF═CHCF₂CF₃); 1,2,3,4,4,4-hexafluoro-1-butene            (CHF═CFCHFCF₃); 1,2,3,3,4,4-hexafluoro-1-butene            (CHF═CFCF₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene            (CHF₂CF═CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene            (CH₂FCF═CFCF₃); 1,1,1,2,4,4-hexafluoro-2-butene            (CHF₂CH═CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene            (CF₃CH═CFCHF₂); 1,1,2,3,3,4-hexafluoro-1-butene            (CF₂═CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene            (CF₂═CFCHFCHF₂);            3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH₂═C(CF₃)₂);            1,1,1,2,4-pentafluoro-2-butene (CH₂FCH═CFCF₃);            1,1,1,3,4-pentafluoro-2-butene (CF₃CH═CFCH₂F);            3,3,4,4,4-pentafluoro-1-butene (CF₃CF₂CH═CH₂);            1,1,1,4,4-pentafluoro-2-butene (CHF₂CH═CHCF₃);            1,1,1,2,3-pentafluoro-2-butene (CH₃CF═CFCF₃);            2,3,3,4,4-pentafluoro-1-butene (CH₂═CFCF₂CHF₂);            1,1,2,4,4-pentafluoro-2-butene (CHF₂CF═CHCHF₂);            1,1,2,3,3-pentafluoro-1-butene (CH₃CF₂CF═CF₂);            1,1,2,3,4-pentafluoro-2-butene (CH₂FCF═CFCHF₂);            1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF₂═C(CF₃)(CH₃));            2-(difluoromethyl)-3,3,3-trifluoro-1-propene            (CH₂═C(CHF₂)(CF₃)); 2,3,4,4,4-pentafluoro-1-butene            (CH₂═CFCHFCF₃); 1,2,4,4,4-pentafluoro-1-butene            (CHF═CFCH₂CF₃); 1,3,4,4,4-pentafluoro-1-butene            (CHF═CHCHFCF₃); 1,3,3,4,4-pentafluoro-1-butene            (CHF═CHCF₂CHF₂); 1,2,3,4,4-pentafluoro-1-butene            (CHF═CFCHFCHF₂); 3,3,4,4-tetrafluoro-1-butene            (CH₂═CHCF₂CHF₂); 1,1-difluoro-2-(difluoromethyl)-1-propene            (CF₂═C(CHF₂)(CH₃)); 1,3,3,3-tetrafluoro-2-methyl-1-propene            (CHF═C(CF₃)(CH₃)); 2-difluoromethyl-3,3-difluoro-1-propene            (CH₂═C(CHF₂)₂); 1,1,1,2-tetrafluoro-2-butene (CF₃CF═CHCH₃);            1,1,1,3-tetrafluoro-2-butene (CH₃CF═CHCF₃);            1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF₃CF═CFCF₂CF₃);            1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF₂═CFCF₂CF₂CF₃);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene            ((CF₃)₂C═CHCF₃); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene            (CF₃CF═CHCF₂CF₃); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene            (CF₃CH═CFCF₂CF₃); 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene            (CHF═CFCF₂CF₂CF₃); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene            (CF₂═CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene            (CF₂═CFCF₂CF₂CHF₂); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene            (CHF₂CF═CFCF₂CF₃); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene            (CF₃CF═CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene            (CF₃CF═CFCHFCF₃);            1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CHF═CFCF(CF₃)₂);            1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CFCH(CF₃) 2);            1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene            (CF₃CH═C(CF₃)₂);            1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CHCF(CF₃)₂); 2,3,3,4,4,5,5,5-octafluoro-1-pentene            (CH₂═CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1-pentene            (CHF═CFCF₂CF₂CHF₂);            3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene            (CH₂═C(CF₃)CF₂CF₃);            1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene            (CF₂═CHCH(CF₃)₂);            1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene            (CHF═CHCF(CF₃)₂);            1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene            (CF₂═C(CF₃)CH₂CF₃);            3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            ((CF₃)₂CFCH═CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene            (CF₃CF₂CF₂CH═CH₂); 2,3,3,4,4,5,5-heptafluoro-1-pentene            (CH₂═CFCF₂CF₂CHF₂); 1,1,3,3,5,5,5-heptafluoro-1-butene            (CF₂═CHCF₂CH₂CF₃);            1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene            (CF₃CF═C(CF₃)(CH₃));            2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            (CH₂═CFCH(CF₃)₂);            1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene            (CHF═CHCH(CF₃)₂);            1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene            (CH₂FCH═C(CF₃)₂);            1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene            (CH₃CF═C(CF₃)₂);            1,1,1-trifluoro-2-(trifluoromethyl)-2-butene            ((CF₃)₂C═CHCH₃); 3,4,4,5,5,5-hexafluoro-2-pentene            (CF₃CF₂CF═CHCH₃); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene            (CF₃C(CH₃)═CHCF₃); 3,3,4,5,5,5-hexafluoro-1-pentene            (CH₂═CHCF₂CHFCF₃);            3-(trifluoromethyl)-4,4,4-trifluoro-1-butene            (CH₂═C(CF₃)CH₂CF₃);            1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene            (CF₃(CF₂)₃CF═CF₂);            1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene            (CF₃CF₂CF═CFCF₂CF₃);            1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene            ((CF₃)₂C═C(CF₃)₂);            1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene            ((CF₃)₂CFCF═CFCF₃);            1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene            ((CF₃)₂C═CHC₂F₅);            1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene            ((CF₃)₂CFCF═CHCF₃); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene            (CF₃CF₂CF₂CF₂CH═CH₂);            4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene            (CH₂═CHC(CF₃)₃);            1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene            ((CF₃)₂C═C(CH₃)(CF₃));            2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene            (CH₂═CFCF₂CH(CF₃)₂);            1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene            (CF₃CF═C(CH₃)CF₂CF₃);            1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene            (CF₃CH═CHCH(CF₃)₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene            (CF₃CF₂CF₂CF═CHCH₃); 3,3,4,4,5,5,6,6-octafluoro-1-hexene            (CH₂═CHCF₂CF₂CF₂CHF₂);            1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene            ((CF₃)₂C═CHCF₂CH₃);            4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene            (CH₂═C(CF₃)CH₂C₂F₅);            3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene            (CF₃CF₂CF₂C(CH₃)═CH₂); 4,4,5,5,6,6,6-heptafluoro-2-hexene            (CF₃CF₂CF₂CH═CHCH₃); 4,4,5,5,6,6,6-heptafluoro-1-hexene            (CH₂═CHCH₂CF₂C₂F₅); 1,1,1,2,2,3,4-heptafluoro-3-hexene            (CF₃CF₂CF═CFC₂H₅);            4,5,5,5-tetrafluoro-4-trifluoromethyl-1-pentene            (CH₂═CHCH₂CF(CF₃)₂);            1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene            (CF₃CF═CHCH(CF₃)(CH₃));            1,1,1,3-tetrafluoro-2-trifluoromethyl-2-pentene            ((CF₃)₂C═CFC₂H₅);            1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene            (CF₃CF═CFCF₂CF₂C₂F₅);            1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene            (CF₃CF₂CF═CFCF₂C₂F₅);            1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene            (CF₃CH═CFCF₂CF₂C₂F₅);            1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene            (CF₃CF═CHCF₂CF₂C₂F₅);            1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene            (CF₃CF₂CH═CFCF₂C₂F₅);            1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene            (CF₃CF₂CF═CHCF₂C₂F₅); CF₂═CFOCF₂CF₃ (PEVE); CF₂═CFOCF₃            (PMVE) and combinations thereof.

The method for producing heating or cooling may be used in stationaryair-conditioning, heat pumps or mobile air-conditioning andrefrigeration systems. Stationary air-conditioning and heat pumpapplications include window, ductless, ducted, packaged terminal,chillers and commercial, including packaged rooftop. Refrigerationapplications include domestic or home refrigerators and freezers, icemachines, self-contained coolers and freezers, walk-in coolers andfreezers and transport refrigeration systems.

The compositions of the present invention may additionally be used inair-conditioning, heating and refrigeration systems that employ fin andtube heat exchangers, microchannel heat exchangers and vertical orhorizontal single pass tube or plate type heat exchangers.

Conventional microchannel heat exchangers may not be ideal for the lowpressure refrigerant compositions of the present invention. The lowoperating pressure and density result in high flow velocities and highfrictional losses in all components. In these cases, the evaporatordesign may be modified. Rather than several microchannel slabs connectedin series (with respect to the refrigerant path) a single slab/singlepass heat exchanger arrangement may be used. Therefore, a preferred heatexchanger for the refrigerant or heat transfer fluid compositions of thepresent invention is a single slab/single pass heat exchanger.

The present invention further relates to a process for producing coolingcomprising evaporating the fluoroolefin compositions of the presentinvention in the vicinity of a body to be cooled, and thereaftercondensing said compositions.

The present invention further relates to a process for producing heatcomprising condensing the fluoroolefin compositions of the presentinvention in the vicinity of a body to be heated, and thereafterevaporating said compositions.

The present invention further relates to a process to produce coolingcomprising compressing a composition comprising at least onefluoroolefin in a centrifugal compressor, condensing said composition,and thereafter evaporating said composition in the vicinity of a body tobe cooled. Additionally, the centrifugal compressor of the inventivemethod may be a multi-stage centrifugal compressor and preferably a2-stage centrifugal compressor.

The present invention further relates to a process to produce cooling ina refrigeration apparatus, air-conditioning apparatus, or heat pumpapparatus, wherein said apparatus comprises at least one singleslab/single pass heat exchanger, said process comprising condensing acomposition of the present invention, and thereafter evaporating saidcomposition in the vicinity of a body to be cooled.

The compositions of the present invention are particularly useful insmall turbine centrifugal compressors (mini-centrifugal compressors),which can be used in auto and window air-conditioning, heat pumps, ortransport refrigeration, as well as other applications. These highefficiency mini-centrifugal compressors may be driven by an electricmotor and can therefore be operated independently of the engine speed. Aconstant compressor speed allows the system to provide a relativelyconstant cooling capacity at all engine speeds. This provides anopportunity for efficiency improvements especially at higher enginespeeds as compared to a conventional R-134a automobile air-conditioningsystem. When the cycling operation of conventional systems at highdriving speeds is taken into account, the advantage of these lowpressure systems becomes even greater.

Alternatively, rather than use electrical power, the mini-centrifugalcompressor may be powered by an engine exhaust gas driven turbine or aratioed gear drive assembly with ratioed belt drive. The electricalpower available in current automobile design is about 14 volts, but thenew mini-centrifugal compressor requires electrical power of about 50volts. Therefore, use of an alternative power source would beadvantageous. A refrigeration apparatus or air-conditioning apparatuspowered by an engine exhaust gas driven turbine is described in detailin U.S. patent application Ser. No. 11/367,517, filed Mar. 3, 2006. Arefrigeration apparatus or air-conditioning apparatus powered by aratioed gear drive assembly is described in detail in U.S. patentapplication Ser. No. 11/378,832, filed Mar. 17, 2006.

The present invention further relates to a process to produce coolingcomprising compressing a composition of the present invention, in amini-centrifugal compressor powered by an engine exhaust gas driventurbine; condensing said composition; and thereafter evaporating saidcomposition in the vicinity of a body to be cooled.

The present invention further relates to a process to produce coolingcomprising compressing a composition of the present invention, in amini-centrifugal compressor powered by a ratioed gear drive assemblywith a ratioed belt drive; condensing said composition; and thereafterevaporating said composition in the vicinity of a body to be cooled.

The present invention relates to a process to produce cooling in arefrigeration apparatus, air-conditioning apparatus, or heat pumpapparatus, wherein said apparatus comprises at least one singleslab/single pass heat exchanger, said process comprising compressing acomposition of the present invention, in a centrifugal compressor,condensing said composition, and thereafter evaporating said compositionin the vicinity of a body to be cooled.

The present invention further relates to a method for replacing orsubstituting for a refrigerant composition having a GWP of about 150 ormore, or a high GWP refrigerant, with a composition having a lower GWP.One method comprises providing a composition comprising at least onefluoroolefin of the present invention as the replacement. In anotherembodiment of the present invention the refrigerant or heat transferfluid composition of the present invention, having a lower GWP than thecomposition being replaced or substituted is introduced into therefrigeration, air conditioning or heat pump apparatus. In some cases,the high GWP refrigerant present in the apparatus will need to beremoved from the apparatus before introduction of the lower GWPcompositions. In other cases, the fluoroolefin compositions of thepresent invention may be introduced into the apparatus while the highGWP refrigerant is present.

Global warming potentials (GWPs) are an index for estimating relativeglobal warming contribution due to atmospheric emission of a kilogram ofa particular greenhouse gas compared to emission of a kilogram of carbondioxide. GWP can be calculated for different time horizons showing theeffect of atmospheric lifetime for a given gas. The GWP for the 100 yeartime horizon is commonly the value referenced.

A high GWP refrigerant would be any compound capable of functioning as arefrigerant or heat transfer fluid having a GWP at the 100 year timehorizon of about 1000 or greater, alternatively 500 or greater, 150 orgreater, 100 or greater, or 50 or greater. Refrigerants and heattransfer fluids that are in need of replacement, based upon GWPcalculations published by the Intergovernmental Panel on Climate Change(IPCC), include but are not limited to HFC-134a(1,1,1,2-tetrafluoroethane).

The present invention will provide compositions that have zero or lowozone depletion potential and low global warming potential (GWP). Thefluoroolefins of the present invention or mixtures of fluoroolefins ofthis invention with other refrigerants will have global warmingpotentials that are less than many hydrofluorocarbon refrigerantscurrently in use. Typically, the fluoroolefins of the present inventionare expected to have GWP of less than about 25. One aspect of thepresent invention is to provide a refrigerant with a global warmingpotential of less than 1000, less than 500, less than 150, less than100, or less than 50. Another aspect of the present invention is toreduce the net GWP of refrigerant mixtures by adding fluoroolefins tosaid mixtures.

The present invention further relates to a method for lowering the GWPof a refrigerant or heat transfer fluid, said method comprisingcombining said refrigerant or heat transfer fluid with at least onefluoroolefin of the present invention. In another embodiment, the methodfor lowering the global warming potential comprises combining said firstcomposition with a composition comprising at least one fluorolefin, toproduce a second composition suitable for use as a refrigerant or heattransfer fluid, and wherein said second composition has a lower globalwarming potential than said first composition. It may be determined thatthe GWP of a mixture or combination of compounds may be calculated as aweighted average of the GWP for each of the pure compounds.

The present invention further relates to a method of using thecomposition of the present invention comprising at least onefluoroolefin to lower global warming potential of an originalrefrigerant or heat transfer fluid composition, said method comprisingcombining said original refrigerant or heat transfer fluid compositionwith the composition of the present invention comprising at least onefluoroolefin, to produce a second refrigerant or heat transfer fluidcomposition wherein said second refrigerant or heat transfer fluidcomposition has a lower global warming potential than said originalrefrigerant or heat transfer fluid composition.

The present invention further relates to a method for reducing the GWPof an original refrigerant or heat transfer fluid composition in arefrigeration, air-conditioning or heat pump apparatus, wherein saidoriginal refrigerant or heat transfer fluid has a GWP of about 150 orhigher; said method comprising introducing a second, lower GWPrefrigerant or heat transfer fluid composition of the present inventioninto said refrigeration, air-conditioning or heat pump apparatus.

The present method for reducing the GWP of an original refrigerant mayfurther comprise removing the original refrigerant or heat transferfluid composition from said refrigeration, air-conditioning or heat pumpapparatus before the second, lower GWP refrigerant or heat transferfluid is introduced.

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition with a secondrefrigerant or heat transfer fluid composition comprising providing acomposition of the present invention as the second refrigerant or heattransfer fluid composition. An original refrigerant may be anyrefrigerant being used in a refrigeration, air-conditioning or heat pumpapparatus in need of replacement

The original refrigerant or heat transfer fluid needing replacement maybe any of hydrofluorocarbon refrigerants, chlorofluorocarbonrefrigerants, hydrochlorofluorocarbon, refrigerants, fluoroetherrefrigerants, or blends of refrigerant compounds.

The hydrofluorocarbon refrigerants of the present invention which mayneed replacing include but are not limited to: CHF₃ (HFC-23), CH₂F₂(HFC-32), CH₃F (HFC-41), CHF₂CF₃ (HFC-125), CHF₂CHF₂ (HFC-134), CH₂FCF₃(HFC-134a), CHF₂CH₂F (HFC143), CF₃CH₃ (HFC-143a), CHF₂CH₃ (HFC-152a),CH₂FCH₃ (HFC-161), CHF₂CF₂CF₃ (HFC-227ca), CF₃CFHCF₃ (HFC-227ea),CHF₂CF₂CHF₂ (HFC-236ca), CH₂FCF₂CF₃ (HFC-236cb), CHF₂CHFCF₃ (HFC-236ea),CF₃CH₂CF₃ (HFC-236fa), CH₂FCF₂CHF₂ (HFC-245ca), CH₃CF₂CF₃ (HFC-245cb),CHF₂CHFCHF₂ (HFC-245ea), CH₂FCHFCF₃ (HFC-245eb), CHF₂CH₂CF₃ (HFC-245fa),CH₂FCF₂CH₂F (HFC-254ca), CH₃CF₂CHF₂ (HFC-254cb), CH₂FCHFCHF₂(HFC-254ea), CH₃CHFCF₃ (HFC-254eb), CHF₂CH₂CHF₂ (HFC-254fa), CH₂FCH₂CF₃(HFC-254fb), CF₃CH₂CH₃ (HFC-263fb), CH₃CF₂CH₂F (HFC-263ca), CH₃CF₂CH₃(HFC-272ca), CH₃CHFCH₂F (HFC-272ea), CH₂FCH₂CH₂F (HFC-272fa), CH₃CH₂CF₂H(HFC-272fb), CH₃CHFCH_(3 (HFC-)281ea), CH₃CH₂CH₂F (HFC-281fa),CHF₂CF₂CF₂CF₂H (HFC-338pcc), CF₃CH₂CF₂CH₃ (HFC-365mfc), CF₃CHFCHFCF₂CF₃(HFC-43-10mee). These hydrofluorocarbon refrigerants are availablecommercially or may be prepared by methods known in the art.

Hydrofluorocarbon refrigerants of the present invention may furthercomprise the azeotropic, azeotrope-like and non-azeotropic compositions,including HFC-125/HFC-143a/HFC-134a (known by the ASHRAE designation,R404 or R404A), HFC-32/HFC-125/HFC-134a (known by ASHRAE designations,R407 or R407A, R407B, or R407C), HFC-32/HFC-125 (R410 or R410A), andHFC-125/HFC-143a (known by the ASHRAE designation: R507 or R507A), R413A(a blend of R134a/R218/isobutane), R423A (a blend of R134a/R227ea),R507A (a blend of R125/R143a), and others.

Chlorofluorocarbon refrigerants of the present invention which may needreplacing include R22 (CHF₂Cl), R123 (CHCl₂CF₃), R124 (CHClFCF₃), R502(being a blend of CFC-115 (CClF₂CF₃) and R22), R503 (being a blend ofR23/R13 (CClF₃)), and others.

Hydrochlorofluorocarbons of the present invention which may needreplacing include R12 (CF₂Cl₂), R11 (CCl₃F), R113 (CCl₂FCClF₂), R114(CF₂ClCF₂Cl), R401A or R401B (being blends of R22/R152a/R124), R408A (ablend of R22/R125/R143a), and others,

The fluoroether refrigerants of the present invention which may needreplacing may comprise compounds similar to hydrofluorocarbons, whichalso contain at least one ether group oxygen atom. The fluoroetherrefrigerants include but are not limited to C₄F₉OCH₃, and C₄F₉OC₂H₅(both available commercially).

The original refrigerant or heat transfer fluid compositions of thepresent invention which may need replacement may optionally furthercomprise combinations of refrigerants that contain up to 10 weightpercent of dimethyl ether, or at least one C₃ to C₅ hydrocarbon, e.g.,propane, propylene, cyclopropane, n-butane, isobutane, n-pentane,cyclopentane and neopentane (2,2-dimethylpropane). Examples ofrefrigerants containing such C₃ to C₅ hydrocarbons are azeotrope-likecompositions of HCFC-22/HFC-125/propane (known by the ASHRAEdesignation, R402 or R402A and R402B), HCFC-22/octafluoropropane/propane(known by the ASHRAE designation, R403 or R403A and R403B),octafluoropropane/HFC-134a/isobutane (known by the ASHRAE designation,R413 or R413A), HCFC-22/HCFC-124/HCFC-142b/isobutane (known by theASHRAE designation, R414 or R414A and R414B), HFC-134a/HCFC-124/n-butane(known by the ASHRAE designation, R416 or R416A),HFC-125/HFC-134a/n-butane (known by the ASHRAE designation, R417 orR417A), HFC-125/HFC-134a/dimethyl ether (known by the ASHRAEdesignation, R419 or R419A), and HFC-125/HFC-134a/isobutane (known byASHRAE designation, R422, R422A, R422B, R422C, R422D).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R134a (HFC-134a, 1,1,1,2-tetrafluoroethane, CF₃CH₂F)in refrigeration apparatus, air-conditioning apparatus, or heat pumpapparatus, wherein said method comprises substituting R134a with asecond refrigerant or heat transfer fluid composition comprising atleast one compound selected from the group consisting of trifluoromethyltrifluorovinyl ether (PMVE).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R152a (HFC-152a, 1,1-difluoroethane, CHF₂CH₃) inrefrigeration apparatus, air-conditioning apparatus, or heat pumpapparatus, wherein said method comprises substituting R152a with asecond refrigerant or heat transfer fluid composition comprising atleast one compound selected from the group consisting ofE-1,3,3,3-tetrafluoropropene (E-HFC-1234ze),1,2,3,3,3-pentafluoropropene (HFC-1225ye), 2,3,3,3-tetrafluoropropene(HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyltrifluorovinyl ether (PMVE).

The present invention further relates to a method for replacing R227ea(HFC-227ea, 1,1,1,2,3,3,3-heptafluoropropane, CF₃CHFCF₃) inrefrigeration apparatus, air-conditioning apparatus, or heat pumpapparatus, wherein said method comprises providing as a substitute acomposition comprising at least one compound selected from the groupconsisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze),1,2,3,3,3-pentafluoropropene (HFC-1225ye), 2,3,3,3-tetrafluoropropene(HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyltrifluorovinyl ether (PMVE).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R113 (CFC-113, 1,1,2-trichloro-1,2,2-trifluoroethane,CFCl₂CF₂Cl) in refrigeration apparatus, air-conditioning apparatus, orheat pump apparatus, wherein said method comprises substituting a secondrefrigerant or heat transfer fluid composition comprising at least onecompound selected from the group consisting of1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-butene(HFC-152-11mmyyz);1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene(HFC-152-11mmtz); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene(HFC-151-12mcy); 1,1,1,3-tetrafluoro-2-butene (HFC-1354mzy);1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene(HFC-151-12mmtt); 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene(FC-C151-10y); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene(HFC-1567fts); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (PFBE);4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC-1567szz);1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (F13E);1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene(HFC-151-12mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R43-10mee (HFC-43-10mee),1,1,1,2,3,4,4,5,5,5-decafluoropentane, CF₃CHFCHFCF₂CF₃) in refrigerationapparatus, air-conditioning apparatus, or heat pump apparatus, whereinsaid method comprises substituting a second refrigerant or heat transferfluid composition comprising at least one compound selected from thegroup consisting of1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-butene(HFC-152-11mmyyz);1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene(HFC-152-11mmtz); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene(HFC-151-12mcy); 1,1,1,3-tetrafluoro-2-butene (HFC-1354mzy);1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene(HFC-151-12mmtt); 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene(FC-C151-10y); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene(HFC-1567fts); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (PFBE);4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC-1567szz);1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (F13E);1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene(HFC-151-12mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being C₄F₉OCH₃ (perfluorobutyl methyl ether) inrefrigeration apparatus, air-conditioning apparatus, or heat pumpapparatus, wherein said method comprises substituting a secondrefrigerant or heat transfer fluid composition comprising at least onecompound selected from the group consisting of1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-butene(HFC-152-11mmyyz);1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene(HFC-152-11mmtz); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene(HFC-151-12mcy); 1,1,1,3-tetrafluoro-2-butene (HFC-1354mzy);1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene(HFC-151-12mmtt); 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene(FC-C151-10y); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene(HFC-1567fts); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (PFBE);4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC-1567szz);1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (F13E);1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene(HFC-151-12mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R365mfc (HFC-365mfc, 1,1,1,3,3-pentafluorobutane,CF₃CH₂CF₂CH₃) in refrigeration apparatus, air-conditioning apparatus, orheat pump apparatus, wherein said method comprises substituting a secondrefrigerant or heat transfer fluid composition comprising at least onecompound selected from the group consisting of1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-butene(HFC-152-11mmyyz);1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene(HFC-152-11mmtz); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene(HFC-151-12mcy); 1,1,1,3-tetrafluoro-2-butene (HFC-1354mzy);1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene(HFC-151-12mmtt); 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene(FC-C151-10y); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene(HFC-1567fts); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (PFBE);4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC-1567szz);1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (F13E);1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene(HFC-151-12mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R11 (CFC-11, trichlorofluoromethane, CFCl₃) inrefrigeration apparatus, air-conditioning apparatus, or heat pumpapparatus, wherein said method comprises substituting a secondrefrigerant or heat transfer fluid composition comprising at least onecompound selected from the group consisting of1,2,3,3,4,4,5,5-octafluorocyclopentene (FC-C1418y);1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (FC-141-10myy);1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429myz);1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429mzy);3,3,4,4,5,5,5-heptafluoro-1-pentene (HFC-1447fz);1,1,1,4,4,4-hexafluoro-2-butene (F11E);1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (HFC-1429mzt); and1,1,1,4,4,5,5,5-octafluoro-2-pentene (F12E).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R123 (HCFC-123, 2,2-dichloro-1,1,1-trifluoroethane,CF₃CHCl₂) in refrigeration apparatus, air-conditioning apparatus, orheat pump apparatus, wherein said method comprises substituting a secondrefrigerant or heat transfer fluid composition comprising at least onecompound selected from the group consisting of1,2,3,3,4,4,5,5-octafluorocyclopentene (FC-C1418y);1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (FC-141-10myy);1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429myz);1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429mzy);3,3,4,4,5,5,5-heptafluoro-1-pentene (HFC-1447fz);1,1,1,4,4,4-hexafluoro-2-butene (F11E);1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (HFC-1429mzt); and1,1,1,4,4,5,5,5-octafluoro-2-pentene (F12E).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R245fa (HFC-245fa, 1,1,1,3,3-pentafluoropropane,CF₃CH₂CHF₂) in refrigeration apparatus, air-conditioning apparatus, orheat pump apparatus, wherein said method comprises substituting a secondrefrigerant or heat transfer fluid composition comprising at least onecompound selected from the group consisting of 2,3,3-trifluoropropene(HFC-1243yf); 1,1,1,4,4,4-hexafluoro-2-butene (F11E);1,3,3,3-tetrafluoropropene (HFC-1234ze);1,1,1,2,4,4,4-heptafluoro-2-butene (HFC-1327my);1,2,3,3-tetrafluoropropene (HFC-1234ye); and pentafluoroethyltrifluorovinyl ether (PEVE).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R114 (CFC-114, 1,2-dichloro-1,1,2,2-tetrafluoroethane,CFCl₂CF₂Cl) in refrigeration apparatus, air-conditioning apparatus, orheat pump apparatus, wherein said method comprises substituting a secondrefrigerant or heat transfer fluid composition comprising at least onecompound selected from the group consisting of1,1,1,2,3,4,4,4-octafluoro-2-butene (FC-1318my);1,2,3,3,4,4-hexafluorocyclobutene (FC-C1316cc);2,3,3,4,4,4-hexafluoro-1-butene (HFC-1336yf); and3,3,4,4,4-pentafluoro-1-butene (HFC-1345fz).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R236fa (HFC-236fa, 1,1,1,3,3,3-hexafluoropropane,CF₃CH₂CF₃) in refrigeration apparatus, air-conditioning apparatus, orheat pump apparatus, wherein said method comprises substituting a secondrefrigerant or heat transfer fluid composition comprising at least onecompound selected from the group consisting of1,1,1,2,3,4,4,4-octafluoro-2-butene (FC-1318my);1,2,3,3,4,4-hexafluorocyclobutene (FC-C1316cc);2,3,3,4,4,4-hexafluoro-1-butene (HFC-1336yf); and3,3,4,4,4-pentafluoro-1-butene (HFC-1345fz).

The present invention relates to a method for replacing an originalrefrigerant or heat transfer fluid composition, said originalcomposition being R401A in refrigeration apparatus, air-conditioningapparatus, or heat pump apparatus, wherein said method comprisessubstituting a second refrigerant or heat transfer fluid compositioncomprising at least one compound selected from the group consisting ofE-1,3,3,3-tetrafluoropropene (E-HFC-1234ze);1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene(HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE). R401A is the ASHRAE designation for arefrigerant blend containing about 53 weight percent HCFC-22(chlorodifluoromethane, CHF₂Cl), about 13 weight percent HFC-152a(1,1-difluoroethane, CHF₂CH₃), and about 34 weight percent HCFC-124(2-chloro-1,1,1,2-tetrafluoroethane, CF₃CHClF).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R401B in refrigeration apparatus, air-conditioningapparatus, or heat pump apparatus, wherein said method comprisessubstituting a second refrigerant or heat transfer fluid compositioncomprising at least one compound selected from the group consisting ofE-1,3,3,3-tetrafluoropropene (E-HFC-1234ze);1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene(HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE). R401B is the ASHRAE designation for arefrigerant blend containing about 61 weight percent HCFC-22(chlorodifluoromethane, CHF₂Cl), about 11 weight percent HFC-152a(1,1-difluoroethane, CHF₂CH₃), and about 28 weight percent HCFC-124(2-chloro-1,1,1,2-tetrafluoroethane, CF₃CHClF).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R409A in refrigeration apparatus, air-conditioningapparatus, or heat pump apparatus, wherein said method comprisessubstituting a second refrigerant or heat transfer fluid compositioncomprising at least one compound selected from the group consisting ofE-1,3,3,3-tetrafluoropropene (E-HFC-1234ze);1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene(HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE). R409A is the ASHRAE designation for arefrigerant blend containing about 60 weight percent HCFC-22(chlorodifluoromethane, CHF₂Cl), about 25 weight percent HCFC-124(2-chloro-1,1,1,2-tetrafluoroethane, CF₃CHClF), and about 15 weightpercent HCFC-142b (1-chloro-1,1-difluoroethane, CF₂ClCH₃).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R409B in refrigeration apparatus, air-conditioningapparatus, or heat pump apparatus, wherein said method comprisessubstituting a second refrigerant or heat transfer fluid compositioncomprising at least one compound selected from the group consisting ofE-1,3,3,3-tetrafluoropropene (E-HFC-1234ze);1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene(HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE). R409B is the ASHRAE designation for arefrigerant blend containing about 65 weight percent HCFC-22(chlorodifluoromethane, CHF₂Cl), about 25 weight percent HCFC-124(2-chloro-1,1,1,2-tetrafluoroethane, CF₃CHClF), and about 10 weightpercent HCFC-142b (1-chloro-1,1-difluoroethane, CF₂ClCH₃).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R414B in refrigeration apparatus, air-conditioningapparatus, or heat pump apparatus, wherein said method comprisessubstituting a second refrigerant or heat transfer fluid compositioncomprising at least one compound selected from the group consisting ofE-1,3,3,3-tetrafluoropropene (E-HFC-1234ze),1,2,3,3,3-pentafluoropropene (HFC-1225ye), 2,3,3,3-tetrafluoropropene(HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyltrifluorovinyl ether (PMVE). R414B is the ASHRAE designation for arefrigerant blend containing about 50 weight percent HCFC-22(chlorodifluoromethane, CHF₂Cl), about 39 weight percent HCFC-124(2-chloro-1,1,1,2-tetrafluoroethane, CF₃CHClF), about 1.5 weight percentisobutane (R600a, CH₃CH(CH₃)CH₃) and about 9.5 weight percent HCFC-142b(1-chloro-1,1-difluoroethane, CF₂ClCH₃).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R416A in refrigeration apparatus, air-conditioningapparatus, or heat pump apparatus, wherein said method comprisessubstituting a second refrigerant or heat transfer fluid compositioncomprising at least one compound selected from the group consisting ofE-1,3,3,3-tetrafluoropropene (E-HFC-1234ze);1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene(HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE). R416A is the ASHRAE designation for arefrigerant blend containing about 59 weight percent HFC-134a(1,1,1,2-tetrafluoroethane, CF₃CH₂F)), about 39.5 weight percentHCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CF₃CHClF), and about 1.5weight percent n-butane (CH₃CH₂CH₂CH₃).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R12 (CFC-12, dichlorodifluoromethane, CF₂Cl₂) inrefrigeration apparatus, air-conditioning apparatus, or heat pumpapparatus, wherein said method comprises substituting a secondrefrigerant or heat transfer fluid composition comprising at least onecompound selected from the group consisting of1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene(HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE).

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition, said originalcomposition being R500 in refrigeration apparatus, air-conditioningapparatus, or heat pump apparatus, wherein said method comprisessubstituting a second refrigerant or heat transfer fluid compositioncomprising at least one compound selected from the group consisting of1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene(HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyltrifluorovinyl ether (PMVE). R500 is the ASHRAE designation for anazeotropic refrigerant blend containing about 73.8 weight percent R12((CFC-12, dichlorodifluoromethane, CF₂Cl₂) and about 26.2 weight percentR152a (HFC-152a, 1,1-difluoroethane, CHF₂CH₃).

The present invention relates to a method for replacing an originalrefrigerant or heat transfer fluid composition wherein the originalrefrigerant or heat transfer fluid composition is R134a or R12 andwherein said R134a or R12 is substituted by a second refrigerant or heattransfer fluid composition comprising about 1.0 weight percent to about37 weight percent HFC-32 and about 99 weight percent to about 63 weightpercent HFC-1225ye. In another embodiment, the second refrigerant orheat transfer fluid composition may comprise about 1.0 weight percent toabout 10 weight percent HFC-32 and about 99 weight percent to about 90weight percent HFC-1225ye.

The present invention relates to a method for replacing an originalrefrigerant or heat transfer fluid composition wherein the originalrefrigerant or heat transfer fluid composition R22, R404A, or R410A andwherein said R22, R404A or R410A is substituted by a second refrigerantor heat transfer fluid composition comprising about 1.0 weight percentto about 37 weight percent HFC-32 and about 99 weight percent to about63 weight percent HFC-1225ye. In another embodiment, the secondrefrigerant or heat transfer fluid composition may comprise about 20weight percent to about 37 weight percent HFC-32 and about 80 weightpercent to about 63 weight percent HFC-1225ye.

The present invention further relates to a method for replacing anoriginal refrigerant or heat transfer fluid composition wherein theoriginal refrigerant or heat transfer fluid composition is R22, R404A,or R410A and wherein said R22, R404A or R410A is substituted by a secondrefrigerant or heat transfer fluid composition comprising about 20weight percent to about 95 weight percent HFC-1225ye, about 1.0 weightpercent to about 65 weight percent HFC-32, and about 1.0 weight percentto about 40 weight percent HFC-125. In another embodiment, the secondrefrigerant or heat transfer fluid composition comprises about 30 weightpercent to about 90 weight percent HFC-1225ye, about 5.0 weight percentto about 55 weight percent HFC-32, and about 1.0 weight percent to about35 weight percent HFC-125. In yet another embodiment, the secondrefrigerant or heat transfer fluid composition comprises about 40 weightpercent to about 85 weight percent HFC-1225ye, about 10 weight percentto about 45 weight percent HFC-32 and about 1.0 weight percent to about28 weight percent HFC-125.

The present invention relates to a method for replacing an originalrefrigerant or heat transfer fluid composition wherein the originalrefrigerant or heat transfer fluid composition is R134a or R12 andwherein said R134a or R12 is substituted by a second refrigerant or heattransfer fluid composition comprising:

HFC-1243zf and HFC-1225ye;

HFC-1243zf, HFC-1225ye, and HFC-125;

HFC-1243zf, HFC-1225ye, and HFC-32; or

HFC-1243zf, HFC-1225ye, HFC-125, and HFC-32.

In all the previously described methods for replacing refrigerants, thefluoroolefins may be used to replace refrigerant in existing equipment.Additionally, the fluoroolefins may be used to replace refrigerant inexisting equipment designed for use of said refrigerant. Additionally,the fluoroolefins may be used to replace refrigerant in existingequipment without the need to change or replace the lubricant.

The present invention relates to a method for reducing the fire hazardin refrigeration apparatus, air-conditioning apparatus, or heat pumpapparatus, said method comprising introducing a composition of thepresent invention into said refrigerant apparatus or air-conditioningapparatus.

Refrigerant that may leak from a refrigeration apparatus,air-conditioning apparatus, or heat pump apparatus, is a major concernwhen considering flammability. Should a leak occur in a refrigerationapparatus or air-conditioning apparatus, refrigerant and potentially asmall amount of lubricant may be released from the system. If thisleaking material comes in contact with an ignition source, a fire mayresult. By fire hazard is meant the probability that a fire may occureither within or in the vicinity of a refrigeration apparatus,air-conditioning apparatus, or heat pump apparatus. Reducing the firehazard in a refrigeration apparatus, air-conditioning apparatus, or heatpump apparatus may be accomplished by using a refrigerant or heattransfer fluid that is not considered flammable as determined anddefined by the methods and standards described previously herein.Additionally, the non-flammable fluoroolefins of the present inventionmay be added to a flammable refrigerant or heat transfer fluid, eitherin the apparatus already or prior to adding to the apparatus. Thenon-flammable fluoroolefins of the present invention reduce theprobability of a fire in the event of a leak and/or reduce the degree offire hazard by reducing the temperature or size of any flame produced.

The present invention further relates to a method for reducing firehazard in or in the vicinity of a refrigeration apparatus,air-conditioning apparatus, or heat pump apparatus, said methodcomprising combining at least one non-flammable fluoroolefin with aflammable refrigerant and introducing the combination into arefrigeration apparatus, air-conditioning apparatus, or heat pumpapparatus.

The present invention further relates to a method for reducing firehazard in or in the vicinity of a refrigeration apparatus,air-conditioning apparatus, or heat pump apparatus, said methodcomprising combining at least one non-flammable fluoroolefin with alubricant and introducing the combination into the refrigerationapparatus, air-conditioning apparatus, or heat pump apparatus comprisingflammable refrigerant.

The present invention further relates to a method for reducing firehazard in or in the vicinity of a refrigeration apparatus,air-conditioning apparatus, or heat pump apparatus, said methodcomprising introducing at least one fluoroolefin into said apparatus.

The present invention further relates to a method of using a flammablerefrigerant in refrigeration apparatus, air-conditioning apparatus, orheat pump apparatus, said method comprising combining said flammablerefrigerant with at least one fluoroolefin.

The present invention further relates to a method for reducingflammability of a flammable refrigerant or heat transfer fluid, saidmethod comprising combining the flammable refrigerant with at least onefluoroolefin.

The present invention further relates to a process for transfer of heatfrom a heat source to a heat sink wherein the compositions of thepresent invention serve as heat transfer fluids. Said process for heattransfer comprises transporting the compositions of the presentinvention from a heat source to a heat sink.

Heat transfer fluids are utilized to transfer, move or remove heat fromone space, location, object or body to a different space, location,object or body by radiation, conduction, or convection. A heat transferfluid may function as a secondary coolant by providing means of transferfor cooling (or heating) from a remote refrigeration (or heating)system. In some systems, the heat transfer fluid may remain in aconstant state throughout the transfer process (i.e., not evaporate orcondense). Alternatively, evaporative cooling processes may utilize heattransfer fluids as well.

A heat source may be defined as any space, location, object or body fromwhich it is desirable to transfer, move or remove heat. Examples of heatsources may be spaces (open or enclosed) requiring refrigeration orcooling, such as refrigerator or freezer cases in a supermarket,building spaces requiring air-conditioning, or the passenger compartmentof an automobile requiring air-conditioning. A heat sink may be definedas any space, location, object or body capable of absorbing heat. Avapor compression refrigeration system is one example of such a heatsink.

EXAMPLES Example 1 Performance Data

Table 7 shows refrigeration performance, as pressure in the evaporator(Evap) and condenser (Cond), discharge temperature (Disch T), energyefficiency (COP), and capacity (Cap), for compounds of the presentinvention as compared to CFC-113, HFC-43-10mee, C₄F₉OCH₃, andHFC-365mfc. The data are based on the following conditions.

Evaporator temperature 40.0° F. (4.4° C.) Condenser temperature 110.0°F. (43.3° C.) Subcool temperature 10.0° F. (5.5° C.) Return gastemperature  75.0° F. (23.8° C.) Compressor efficiency is 70%

TABLE 7 Evap Evap Cond Cond Comp Comp Pres Pres Pres Pres Disch T DischT Cap Cap Compound (Psia) (kPa) (Psia) (kPa) (F.) (C.) COP (Btu/min)(kW) CFC-113 2.7 18.6 12.8 88.3 156.3 69.1 4.18 14.8 0.26 HFC-43-10mee2.0 13.4 10.4 71.9 132.8 56.0 3.94 12.2 0.21 C₄F₉OCH₃ 1.5 10.1 8.3 57.0131.3 55.2 3.93 9.5 0.17 HFC-365mfc 3.6 25.1 16.3 112.1 146.3 63.5 4.1121.4 0.38 1,1,1,3,4,5,5,5-octafluoro-4- 2.1 14.4 10.7 71.9 127.1 52.83.83 12.3 0.24 (trifluoromethyl)-2-butene ((HFC-152-11mmyyz)1,1,1,4,4,5,5,5-octafluoro-2- 2.0 13.4 10.4 71.9 127.3 52.9 3.83 11.80.23 (trifluoromethyl)-2-pentene (HFC-152-11mmtz)1,1,1,2,2,3,4,5,5,6,6,6- 2.5 17.3 12.3 85.1 121.8 49.9 3.69 13.8 0.24dodecafluoro-3-hexene (FC-151-12mcy) 1,1,1,3-tetrafluoro-2-butene 2.517.4 11.6 80.1 162.0 72.2 4.25 15.9 0.28 (HFC-1354mzy)1,1,1,4,4,4-hexafluoro-2,3- 2.0 13.5 10.0 69.2 122.7 50.4 3.73 11.2 0.20bis(trifluoromethyl)-2-butene (FC-151-12mmtt) 1,2,3,3,4,4,5,5,6,6- 2.114.4 10.6 72.9 126.7 52.6 3.84 12.3 0.22 decafluorocyclohexene(FC-C151-10y) 3,3,4,4,5,5,5-heptafluoro-2- 2.0 14.1 9.9 68.5 130.0 54.43.92 12.0 0.21 methyl-1-pentene (HFC-1567fts)3,3,4,4,5,5,6,6,6-nonafluoro-1- 1.6 11.0 8.6 59.4 130.7 54.8 3.92 10.00.18 hexene (PFBE) 4,4,5,5,6,6,6-heptafluoro-2- 1.3 9.2 7.4 51.3 137.858.8 4.04 8.9 0.16 hexene (HFC-1567szz) 1,1,1,4,4,5,5,6,6,6-decafluoro-2.0 13.7 10.7 73.8 131.1 55.1 3.90 12.4 0.22 2-hexene (F13E)1,1,1,2,3,4,5,5,5-nonafluoro- 2.5 17.3 12.3 85.1 121.8 49.9 3.69 13.80.24 4-(trifluoromethyl)-2- pentene (FC-151-12mmzz) 1,1,1,2,2,5,5,6,6,6-2.4 16.6 12.6 86.7 128.0 53.3 3.83 14.4 0.25 decafluoro-3-hexene (F22E)

Example 2 Performance Data

Table 8 shows refrigeration performance, as pressure in the evaporator(Evap) and condenser (Cond), discharge temperature (Disch T), energyefficiency (COP), and capacity (Cap), for compounds of the presentinvention as compared to CFC-11 and HCFC-123. The data are based on thefollowing conditions.

Evaporator temperature 40.0° F. (4.4° C.) Condenser temperature 110.0°F. (43.3° C.) Subcool temperature 10.0° F. (5.5° C.) Return gastemperature  75.0° F. (23.8° C.) Compressor efficiency is 70%

TABLE 8 Evap Evap Cond Cond Comp Comp Pres Pres Pres Pres Disch T DischT Cap Cap Compound (Psia) (kPa) (Psia) (kPa) (F.) (C.) COP (Btu/min)(kW) CFC-11 7.1 49.0 28.0 192.8 190.5 88.1 4.29 41.1 0.72 HCFC-123 5.840.3 25.0 172.4 174.2 79.0 4.25 35.2 0.62 1,2,3,3,4,4,5,5- 6.0 41.6 25.3174.6 131.7 55.4 3.87 31.6 0.55 octafluorocyclopentene (FC-C1418y)1,1,1,2,3,4,4,5,5,5- 7.5 51.8 30.0 206.6 124.9 51.6 3.66 35.3 0.62decafluoro-2-pentene (FC-141-10myy) 1,1,1,2,4,4,5,5,5- 5.5 37.9 23.7163.1 132.0 55.6 3.85 29.0 0.51 nonafluoro-2-pentene (HFC-1429myz)1,1,1,3,4,4,5,5,5- 5.5 37.9 23.7 163.1 132.0 55.6 3.85 29.0 0.51nonafluoro-2-pentene (HFC-1429mzy) 3,3,4,4,5,5,5- 5.4 37.0 23.1 159.3135.3 57.4 3.92 29.0 0.51 heptafluoro-1-pentene (HFC-1447fz)1,1,1,4,4,4-hexafluoro-2- 4.7 32.3 20.8 143.4 150.1 65.6 4.11 27.5 0.48butene (F11E) 1,1,1,4,4,4-hexafluoro-2- 4.8 33.0 21.0 144.9 132.6 55.93.88 25.9 0.45 (trifluoromethyl)-2- butene (HFC-1429mzt)1,1,1,4,4,5,5,5- 5.5 37.9 24.4 168.0 137.0 58.3 3.93 30.6 0.54octafluoro-2-pentene (F12E)

Example 3 Performance Data

Table 9 shows refrigeration performance, as pressure in the evaporator(Evap) and condenser (Cond), discharge temperature (Disch T), energyefficiency (COP), and capacity (Cap), for compounds of the presentinvention as compared to HFC-245fa. The data are based on the followingconditions.

Evaporator temperature 40.0° F. (4.4° C.) Condenser temperature 110.0°F. (43.3° C.) Subcool temperature 10.0° F. (5.5° C.) Return gastemperature  75.0° F. (23.8° C.) Compressor efficiency is 70%

TABLE 9 Evap Evap Cond Cond Comp Comp Pres Pres Pres Pres Disch T DischT Cap Cap Compound (Psia) (kPa) (Psia) (kPa) (F.) (C.) COP (Btu/min)(kW) HFC-245fa 10.0 68.8 38.9 268.5 156.7 69.3 4.10 53.3 0.932,3,3-trifluoropropene 12.6 87.1 45.4 313.0 172.8 78.2 4.19 65.6 1.15(HFC-1243yf) 1,1,1,4,4,4-hexafluoro-2- 12.5 85.9 47.5 327.4 148.8 64.93.99 62.8 1.10 butene (F11E) 1,3,3,3-tetrafluoropropene 12.1 83.4 45.8315.6 178.8 81.6 4.19 65.6 1.15 (HFC-1234ze) 1,1,1,2,4,4,4-heptafluoro-10.5 72.5 39.9 275.0 142.3 61.3 3.94 52.0 0.91 2-butene (HFC-1327my)1,2,3,3-tetrafluoropropene 9.6 66.3 36.9 254.6 176.9 80.5 4.21 53.0 0.93(HFC-1234ye) pentafluoroethyl 13.1 90.4 49.3 339.8 130.7 54.8 3.69 59.31.04 trifluorovinyl ether (PEVE)

Example 4 Performance Data

Table 10 shows refrigeration performance, as pressure in the evaporator(Evap) and condenser (Cond), discharge temperature (Disch T), energyefficiency (COP), and capacity (Cap), for compounds of the presentinvention as compared to CFC-114 and HFC-236fa. The data are based onthe following conditions.

Evaporator temperature 40.0° F. (4.4° C.) Condenser temperature 110.0°F. (43.3° C.) Subcool temperature 10.0° F. (5.5° C.) Return gastemperature  75.0° F. (23.8° C.) Compressor efficiency is 70%

TABLE 10 Evap Evap Cond Cond Comp Comp Pres Pres Pres Pres Disch T DischT Cap Cap Compound (Psia) (kPa) (Psia) (kPa) (F.) (C.) COP (Btu/min)(kW) CFC-114 15.4 106.5 54.3 374.2 147.2 64.0 3.97 72.9 1.28 HFC-236fa18.2 125.8 64.2 442.6 142.8 61.6 3.86 82.9 1.451,1,1,2,3,4,4,4-octafluoro-2- 17.2 118.8 59.1 407.4 131.8 55.4 3.68 72.11.26 butene (FC-1318my) 1,2,3,3,4,4- 16.5 113.5 58.8 405.4 141.1 60.63.90 76.6 1.34 hexafluorocyclobutene (FC-C1316cc)2,3,3,4,4,4-hexafluoro-1- 14.2 98.2 50.2 346.3 139.4 59.7 3.88 65.3 1.14butene (HFC-1336yf) 3,3,4,4,4-pentafluoro-1- 14.8 101.8 53.5 368.5 145.563.1 3.95 70.7 1.24 butene (HFC-1345fz)

Example 5 Performance Data

Table 11 shows refrigeration performance, as pressure in the evaporator(Evap) and condenser (Cond), discharge temperature (Disch T), energyefficiency (COP), and capacity (Cap), for compounds of the presentinvention as compared to HFC-134a, HFC-152a, and HFC-227ea. The data arebased on the following conditions.

Evaporator temperature 40.0° F. (4.4° C.) Condenser temperature 110.0°F. (43.3° C.) Subcool temperature 10.0° F. (5.5° C.) Return gastemperature  75.0° F. (23.8° C.) Compressor efficiency is 70%

TABLE 11 Evap Evap Cond Cond Comp Comp Pres Pres Pres Pres Disch T DischT Cap Cap Compound (Psia) (kPa) (Psia) (kPa) (F.) (C.) COP (Btu/min)(kW) HFC-134a 49.6 341.6 161.2 1111.4 168.9 76.1 3.86 213.3 3.73HFC-152a 46.2 318.8 146.5 1009.9 200.1 93.4 4.02 209.4 3.67 HFC-227ea32.3 222.7 105.5 727.4 142.9 61.6 3.67 129.3 2.262,3,3,3-tetrafluoropropene 47.4 326.7 139.6 962.2 154.8 68.2 3.79 180.53.16 (HFC-1234yf) 3,3,3-trifluoropropene 39.0 268.8 122.0 841.0 166.274.6 3.95 166.3 2.91 (HFC-1243zf) 1,2,3,3,3-pentafluoropropene 36.1248.9 112.9 778.4 157.8 69.9 3.86 148.9 2.61 (HFC-1225ye)E-1,3,3,3-tetrafluoropropene 35.5 245.0 115.1 793.9 162.4 72.4 3.90153.8 2.69 (E-HFC-1234ze) trifluoromethyl trifluorovinyl 39.3 271.1124.0 855.2 140.9 60.5 3.57 147.6 2.58 ether (PMVE)

Example 6 Flammability

Flammable compounds may be identified by testing under ASTM (AmericanSociety of Testing and Materials) E681-01, with an electronic ignitionsource. Such tests of flammability were conducted on compositions of thepresent disclosure at 101 kPa (14.7 psia), 50 percent relative humidity,and the temperature indicated, at various concentrations in air in orderto determine if flammable and if so, find the lower flammability limit(LFL). The results are given in Table 12.

TABLE 12 Temperature Composition (° C.) LFL (vol % in air) HFC-1225ye100 Non-flammable HFC-1234yf 100  5.0 E-HFC-1234ze 100  6.0HFC-1429myz/mzy 23 Non-flammable F12E 23 Non-flammable HFC-1225ye/HFC-60 Non-flammable 32 (65/35 wt %) HFC-1225ye/HFC- 60 Non-flammable 32(63/37 wt %) HFC-1225ye/HFC- 60 13.0 32 (62/38 wt %) HFC-1225ye/HFC- 6013.0 32 (60/40 wt %)

The results indicate that HFC-1234yf and E-HFC-1234ze are flammable,while HFC-1225ye, HFC-1429myz/mzy, and F12E are non-flammable. Formixtures of HFC-1225ye and HFC-32 (which is known to be flammable in thepure state) it has been determined that 37 weight percent HFC-32 is thehighest amount that can be present to maintain the non-flammablecharacteristic. Those compositions comprising fluoroolefins that arenon-flammable are more acceptable candidates as refrigerant or heattransfer fluid compositions.

Example 7 Tip Speed to Develop Pressure

Tip speed can be estimated by making some fundamental relationships forrefrigeration equipment that use centrifugal compressors. The torque animpeller ideally imparts to a gas is defined asT=m*(v ₂ *r ₂ −v ₁ *r ₁)  Equation 1where

-   -   T=torque, Newton-meters    -   m=mass rate of flow, kg/sec    -   v₂=tangential velocity of refrigerant leaving impeller (tip        speed), meters/sec    -   r₂=radius of exit impeller, meters    -   v₁=tangential velocity of refrigerant entering impeller,        meters/sec    -   r₁=radius of inlet of impeller, meters

Assuming the refrigerant enters the impeller in an essentially axialdirection, the tangential component of the velocity v₁=0, thereforeT=m*v ₂ *r ₂  Equation 2

The power required at the shaft is the product of the torque and therotative speedP=T*ω  Equation 3where

P=power, W

ω=angular velocity, radians/s

therefore,P=T*w=m*v ₂ *r ₂*ω  Equation 4

At low refrigerant flow rates, the tip speed of the impeller and thetangential velocity of the refrigerant are nearly identical; thereforer ₂ *ω=v ₂  Equation 5andP=m*v ₂ *v ₂  Equation 6

Another expression for ideal power is the product of the mass rate offlow and the isentropic work of compression,P=m*H _(i)*(1000J/kJ)  Equation 7where

H_(i)=Difference in enthalpy of the refrigerant from a saturated vaporat the evaporating conditions to saturated condensing conditions, kJ/kg.

Combining the two expressions Equation 6 and 7 produces,v ₂ *v ₂=1000*H _(i)  Equation 8

Although Equation 8 is based on some fundamental assumptions, itprovides a good estimate of the tip speed of the impeller and providesan important way to compare tip speeds of refrigerants.

Table 13 below shows theoretical tip speeds that are calculated for1,2,2-trichlorotrifluoroethane (CFC-113) and compositions of the presentinvention. The conditions assumed for this comparison are:

Evaporator temperature 40.0° F. (4.4° C.) Condenser temperature 110.0°F. (43.3° C.) Liquid subcool temperature 10.0° F. (5.5° C.) Return gastemperature  75.0° F. (23.8° C.) Compressor efficiency is 70%

These are typical conditions under which small turbine centrifugalcompressors perform.

TABLE 13 Tip speed Tip speed Hi Hi * 0.7 Hi * 0.7 (V2) relative toCompound Btu/lb Btu/lb KJ/Kg m/s CFC-113 CFC-113 10.92 7.6 17.8 133.3n/a HFC-152-11mmyyz 11.56 8.1 18.8 137.2 103% FC-151-12mcy 11.86 8.319.3 139.0 104% HFC-1354mzy 13.96 9.8 22.7 150.8 113% FC-151-12mmtt11.93 8.4 19.4 139.4 105% FC-C151-10y 12.48 8.7 20.3 142.5 107%HFC-1567fm 14.21 9.9 23.1 152.1 114% PFBE 12.8 9.0 20.8 144.4 108%HFC-1567szz 13.42 9.4 21.9 147.8 111% HFC-1438mzz 11.73 8.2 19.1 138.2104% FC-151-12mmzz 11.86 8.3 19.3 139.0 104% HFC-153-10mczz 12.23 8.619.9 141.1 106%

The example shows that compounds of the present invention have tipspeeds within about 15 percent of CFC-113 and would be effectivereplacements for CFC-113 with minimal compressor design changes. Mostpreferred compositions have tip speeds within about 10 percent ofCFC-113.

Example 8 Refrigeration Performance Data

Table 14 shows the performance of various refrigerant compositions ofthe present invention as compared to HFC-134a. In Table 14, Evap Pres isevaporator pressure, Cond Pres is condenser pressure, Comp Disch T iscompressor discharge temperature, COP is energy efficiency, and CAP iscapacity. The data are based on the following conditions.

Evaporator temperature 40.0° F. (4.4° C.) Condenser temperature 130.0°F. (54.4° C.) Subcool amount 10.0° F. (5.5° C.) Return gas temperature 60.0° F. (15.6° C.) Compressor efficiency is 100%Note that the superheat is included in cooling capacity.

TABLE 14 Evap Evap Cond Cond Comp Comp Pres Pres Pres Pres Disch T DischT Cap Cap Composition (wt %) (Psia) (kPa) (Psia) (kPa) (F.) (C.)(Btu/min) (kW) COP HFC-134a 50.3 346 214 1476 156 68.9 213 3.73 4.41HFC-1225ye 37.6 259 165 1138 146 63.3 162 2.84 4.41 HFC-1225ye/HFC-152a(85/15) 39.8 274 173 1193 151 66.1 173 3.03 4.45 HFC-1225ye/HFC-32(97/3) 43.1 297 184 1269 149 65.0 186 3.26 4.50 HFC-1225ye/HFC-32 (96/4)44.2 305 189 1303 150 65.6 191 3.35 4.51 HFC-1225ye/HFC-32 (95/5) 46.5321 197 1358 151 66.1 200 3.50 4.53 HFC-1225ye/HFC-32 (94/6) 47.3 326200 1379 153 67.2 203 3.56 4.52 HFC-1225ye/HFC-32 (93/7) 48.8 336 2051413 154 67.8 210 3.68 4.53 HFC-1225ye/HFC-32 (90/10) 53.0 365 222 1531157 69.4 227 3.98 4.52 HFC-1243zf/HFC-1225ye (40/60) 40.8 281 172 1186148 64.4 170 2.97 4.39 HFC-1243zf/HFC-1225ye (50/50) 41.8 288 174 1200149 65.0 172 3.02 4.37 HFC-1243zf/HFC-1225ye (60/40) 42.9 296 177 1220149 65.0 175 3.07 4.36 HFC-1243zf/HFC-1225ye (70/30) 44.1 304 180 1241150 65.6 178 3.12 4.35 HFC-1243zf/HFC-1225ye/ 42.7 294 179 1234 148 64.4176 3.09 4.38 HFC-125 (40/56/4) HFC-1243zf/HFC-1225ye/ 43.7 301 181 1248149 65.0 179 3.13 4.37 HFC-125 (50/46/4) HFC-1243zf/HFC-1225ye/ 44.8 309184 1269 149 65.0 182 3.18 4.36 HFC-125 (60/36/4) HFC-1243zf/HFC-1225ye/49.9 344 201 1386 153 67.2 202 3.54 4.40 HFC-125 (70/26/4)HFC-1243zf/HFC-1225ye/ 48.4 334 199 1372 153 67.2 202 3.54 4.47 HFC-32(40/55/5) HFC-1243zf/HFC-1225ye/ 45.6 314 189 1303 151 66.1 190 3.334.44 HFC-32 (42/55/3) HFC-1243zf/HFC-1225ye/ 50.3 347 203 1400 154 67.8206 3.60 4.43 HFC-32 (60/35/5) HFC-1243zf/HFC-1225ye/ 47.7 329 194 1338152 66.7 195 3.41 4.41 HFC-32 (62/35/3) HFC-1243zf/HFC-1225ye/ 44.2 305184 1269 149 65.0 183 3.21 4.41 HFC-125/HFC-32 (40/55/4/1)HFC-1243zf/HFC-1225ye/ 45.3 312 188 1296 150 65.6 188 3.29 4.42HFC-125/HFC-32 (40/55/3/2) HFC-1243zf/HFC-1225ye/ 46.3 319 189 1303 15065.6 188 3.29 4.37 HFC-125/HFC-32 (60/35/4/1) HFC-1243zf/HFC-1225ye/47.3 326 193 1331 151 66.1 192 3.37 4.39 HFC-125/HFC-32 (60/35/3/2)

Several compositions have even higher energy efficiency (COP) thanHFC-134a while maintaining lower or equivalent discharge pressures andtemperatures. Capacity for the compositions listed in Table 14 is alsosimilar to R134a indicating these compositions could be replacementrefrigerants for R134a in refrigeration and air-conditioning, and inmobile air-conditioning applications in particular. Results also showcooling capacity of HFC-1225ye can be improved with addition of othercompounds such as HFC-32.

Example 9 Refrigeration Performance Data

Table 15 shows the performance of various refrigerant compositions ofthe present invention as compared to R404A and R422A. In Table 15, EvapPres is evaporator pressure, Cond Pres is condenser pressure, Comp DischT is compressor discharge temperature, EER is energy efficiency, and CAPis capacity. The data are based on the following conditions.

Evaporator temperature −17.8° C.  Condenser temperature 46.1° C. Subcoolamount  5.5° C. Return gas temperature 15.6° C. Compressor efficiency is70%Note that the superheat is included in cooling capacity.

TABLE 15 Evap Cond P Compr Press Press Disch T CAP wt % (kPa)) (kPa)(C.) (kJ/m3) EER Existing Refrigerant Product R22 267 1774 144 1697 4.99R404A 330 2103 101.1 1769 4.64 R507A 342 2151 100.3 1801 4.61 R422A 3242124 95.0 1699 4.54 Candidate Replacement HFC-32/HFC-1225ye 20/80 2001620 117 1331 4.91 HFC-32/HFC-1225ye 30/70 246 1879 126 1587 4.85HFC-32/HFC-1225ye 40/60 284 2101 134 1788 4.74 HFC-32/HFC-1225ye 35/65256 1948 130.5 1652 4.85 HFC-32/HFC-1225ye 37/63 264 1991 132.2 16944.81 HFC-32/HFC-125/ 10/10/′80 173 1435 107.0 1159 4.97 HFC-1225yeHFC-32/HFC-125/ 15/5.5/79.5 184 1509 111.9 1235 4.97 HFC-1225yeHFC-32/HFC-125/ 24/13.7/62.3 242 1851 119.7 1544 4.85 HFC-1225yeHFC-32/HFC-125/ 25/25/50 276 2041 120.0 1689 4.73 HFC-1225yeHFC-32/HFC-125/ 25/40/35 314 2217 119.0 1840 4.66 HFC-1225yeHFC-32/HFC-125/ 27.5/17.5/55 264 1980 122.8 1653 4.78 HFC-1225yeHFC-32/HFC-125/ 30/10/60 265 1990 125.0 1664 4.78 HFC-1225yeHFC-32/HFC-125/ 30/15/55 276 2046 125.0 1710 4.76 HFC-1225yeHFC-32/HFC-125/ 30/19/51 278 2056 124.8 1724 4.75 HFC-1225yeHFC-32/HFC-125/ 30/20/50 287 2102 124.0 1757 4.73 HFC-1225yeHFC-32/HFC-125/ 30/30/40 311 2218 124.0 1855 4.68 HFC-1225yeHFC-32/HFC-125/ 30/35/35 324 2271 123.0 1906 4.66 HFC-1225yeHFC-32/HFC-125/ 31/20/49 285 2090 125.5 1756 4.74 HFC-1225yeHFC-32/HFC-125/ 33/22/45 298 2157 127.0 1820 4.72 HFC-1225yeHFC-32/HFC-125/ 35/15/50 296 2157 129.0 1820 4.72 HFC-1225yeHFC-32/HFC-125/ 35/20/45 308 2212 129.0 1868 4.70 HFC-1225yeHFC-32/HFC-125/ 35/30/35 332 2321 127.0 1968 4.66 HFC-1225yeHFC-32/HFC-125/ 35/40/25 357 2424 126.0 2068 4.64 HFC-1225yeHFC-32/HFC-125/ 50/30/20 390 2584 138.0 2277 4.54 HFC-1225yeHFC-32/HFC-125/ 40/30/30 353 2418 131.0 2077 4.66 HFC-1225yeHFC-32/HFC-125/ 40/35/25 364 2465 131.0 2124 4.64 HFC-1225yeHFC-32/HFC-125/ 45/30/25 372 2505 135.0 2180 4.66 HFC-1225ye

Several compositions have energy efficiency (EER) comparable top R404Aand R422A. Discharge temperatures are also lower than R404A and R507A.Capacity for the compositions listed in Table 15 is also similar toR404A, R507A, and R422A indicating these compositions could bereplacement refrigerants for R404A, R507A, or R422A in refrigeration andair-conditioning.

Example 10 Refrigeration Performance Data

Table 16 shows the performance of various refrigerant compositions ofthe present invention as compared to HCFC-22 and R410A. In Table 16,Evap Pres is evaporator pressure, Cond Pres is condenser pressure, CompDisch T is compressor discharge temperature, EER is energy efficiency,and CAP is capacity. The data are based on the following conditions.

Evaporator temperature  4° C. Condenser temperature 43° C. Subcoolamount  6° C. Return gas temperature 18° C. Compressor efficiency is 70%Note that the superheat is included in cooling capacity.

TABLE 16 Compr Evap Cond Disch Press Press Temp CAP Existing refrigerantproduct (kPa) (kPa) (C.) (kJ/m3) EER R22 565 1648 90.9 3808 9.97 R410A900 2571 88.1 5488 9.27 Candidate replacement product (Composition wt %)HFC-32/HFC-1225ye (40/60) 630 1948 86.7 4242 9.56 HFC-32/HFC-1225ye(45/55) 666 2041 88.9 4445 9.49 HFC-32/HFC-1225ye (50/50) 701 2127 91.04640 9.45 HFC-32/HFC-1225ye (30/70) 536 1700 82.1 3729 9.73HFC-32/HFC-1225ye (35/65) 575 1805 84.5 3956 9.66 HFC-32/HFC-1225ye(37/63) 590 1845 85.5 4043 9.64 HFC-32/HFC-125/HFC-1225ye 784 2323 94.65087 9.42 (60/5/35) HFC-32/HFC-125/HFC-1225ye 803 2365 94.2 5173 9.42(60/10/30) HFC-32/HFC-125/HFC-1225ye 822 2407 93.9 5256 9.39 (60/15/25)HFC-32/HFC-125/HFC-1225ye 742 2220 90.3 4820 9.42 (50/10/40)HFC-32/HFC-125/HFC-1225ye 721 2173 90.7 4730 9.45 (50/5/45)HFC-32/HFC-125/HFC-1225ye 762 2266 90.0 4911 9.42 (50/15/35)HFC-32/HFC-125/HFC-1225ye 692 2097 85.9 4518 9.45 (40/15/45)HFC-32/HFC-125/HFC-1225ye 671 2047 86.2 4425 9.49 (40/10/50)HFC-32/HFC-125/HFC-1225ye 654 2001 83.8 4304 9.49 (35/15/50)HFC-32/HFC-125/HFC-1225ye 643 1976 85.2 4287 9.54 (37.5/11.5/51)HFC-32/HFC-125/HFC-1225ye 593 1848 83.8 4028 9.62 (34/6/60)HFC-32/HFC-125/HFC-1225ye 548 1732 82.0 3788 9.70 (30/3/67)HFC-32/HFC-125/HFC-1225ye 590 1837 81.7 3980 9.60 (30/12.7/57.3)HFC-32/HFC-125/HFC-1225ye 544 1715 78.7 3713 9.66 (24/13.7/62.3)HFC-32/HFC-125/HFC-1225ye 471 1522 76.9 3329 9.82 (20/5/75)HFC-32/HFC-125/HFC-1225ye 427 1398 74.1 3061 9.89 (15/5.5/79.5)Compositions have energy efficiency (EER) comparable to R22 and R410Awhile maintaining reasonable discharge temperatures. Capacity forcertain compositions listed in Table 16 is also similar to R22indicating these compositions could be replacement refrigerants for R22in refrigeration and air-conditioning. Additionally, there arecompositions listed in Table 16 with capacity approaching or equivalentto that for R410A indicating that those compositions could bereplacement refrigerants for R410A in refrigeration andair-conditioning.

Example 11 Refrigeration Performance Data

Table 17 shows the performance of various refrigerant compositions ofthe present invention as compared to HCFC-22, R410A, R407C, and R417A.In Table 17, Evap Pres is evaporator pressure, Cond Pres is condenserpressure, Comp Disch T is compressor discharge temperature, EER isenergy efficiency, and CAP is capacity. The data are based on thefollowing conditions.

Evaporator temperature  4.4° C. Condenser temperature 54.4° C. Subcoolamount  5.5° C. Return gas temperature 15.6° C. Compressor efficiency is100%Note that the superheat is included in cooling capacity.

TABLE 17 Evap Cond Compr Press Press Disch T CAP wt % (kPa)) (kPa) (C.)(kJ/m³) EER Existing Refrigerant Product R22 573 2149 88.6 3494 14.73R410A 911 3343 89.1 4787 13.07 R407C 567 2309 80.0 3397 14.06 R417A 4941979 67.8 2768 13.78 Candidate Replacement HFC-32/HFC-125/ 30/40/30 7322823 81.1 3937 13.20 HFC-1225ye HFC-32/HFC-125/ 23/25/52 598 2429 78.03409 13.54 HFC-1225ye

Compositions have energy efficiency (EER) comparable to R22, R407C,R417A, and R410A while maintaining low discharge temperatures. Capacityfor the compositions listed in Table 17 is also similar to R22, R407Cand R417A indicating these compositions could be replacementrefrigerants for R22, R407C or R417A in refrigeration andair-conditioning.

What is claimed is:
 1. A refrigerant or heat transfer fluid compositioncomprising 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene and alubricant.
 2. The composition of claim 1, further comprising a flammablerefrigerant.
 3. The composition of claim 2, wherein the flammablerefrigerant is selected from the group consisting of hydrofluorocarbons,fluoroethers, hydrocarbon ethers, hydrocarbons, ammonia and combinationsthereof.
 4. The composition of claim 3, wherein the flammablerefrigerant is selected from the group consisting of difluoromethane(HFC-32); fluoromethane (HFC-41); 1,1,1-trifluoroethane (HFC-143a);1,1,2-trifluoroethane (HFC-143); 1,1-difluoroethane (HFC-152a);fluoroethane (HFC-161); 1,1,1-trifluoropropane (HFC-263fb); 1,1,1,3,3-pentafluorobutane (HFC-365mfc); 1,2,3,3-tetrafluoro-1-propene(HFC-1234ye); 1,3,3,3-tetrafluoro-1-propene (HFC-1234ze);2,3,3,3-tetrafluoro-1-propene (HFC-1234yf);1,1,2,3-tetrafluoro-1-propene (HFC-1234yc);1,1,3,3-tetrafluoro-1-propene (HFC-1234zc); 2,3,3-trifluoro-1-propene(HFC-1243yf); 3,3,3-trifluoro-1-propene (HFC-1243zf);1,1,2-trifluoro-1-propene (HFC-1243yc); 1,1,3-trifluoro-1-propene(HFC-1243zc); 1,2,3-trifluoro-1-propene (HFC-1243ye); and1,3,3-trifluoro-1-propene (HFC-1243ze) C₄F₉OC₂H₅; propane; propylene;cyclopropane; n-butane; isobutane; n-pentane; 2-methylbutane;2,2-dimethylpropane; cyclopentane, cyclobutane; 2,2-dimethylbutane;2,3-dimethylbutane; 2,3-dimethylpentane; 2-methylhexane; 3-methylhexane;2-methylpentane; 3-ethylpentane; 3-methylpentane; cyclohexane;n-heptane; methylcyclopentane; n-hexane; dimethylether; methyl t-butylether; ammonia, and combinations thereof.
 5. The composition of claim 1,wherein said lubricant is selected from the group consisting of mineraloils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes,polyalpha-olefins, polyalkylene glycols, polyvinyl ethers, polyol estersand mixtures thereof.
 6. A process for cooling comprising condensing thecomposition of claim 1 and thereafter evaporating said composition inthe vicinity of a body to be cooled.
 7. A process for heating comprisingevaporating the composition of claim 1 and thereafter condensing saidcomposition in the vicinity of a body to be heated.
 8. A method forproducing heating or cooling in a refrigeration, air-conditioning, orheat pump apparatus, said method comprising introducing the refrigerantor heat transfer fluid composition of claim 1 into said apparatus having(a) a centrifugal compressor; (b) a multi-stage centrifugal compressor;or (c) a single slap/single pass heat exchanger.
 9. A method forreplacing the use of a high global warming potential refrigerant, saidmethod comprising providing the composition of claim 1 in refrigerationair-conditioning, or heat pump apparatus in place of or in combinationwith the high global warming potential refrigerant in said apparatus.10. A method for replacing an original refrigerant or heat transferfluid composition with a second refrigerant or heat transfer fluidcomposition comprising providing a composition of claim 1 as the secondrefrigerant or heat transfer fluid composition.
 11. The method of claim10 wherein: the original refrigerant comprises fluorotrichloromethane(R11) or 2,2-dichloro-1,1,1-trifluoroethane (R123) and the secondrefrigerant comprises1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene.
 12. A method ofusing the composition of claim 1 as a heat transfer fluid composition,said method comprising transporting said composition from a heat sourceto a heat sink.
 13. A refrigeration, air-conditioning or heat pumpapparatus containing a composition of claim
 1. 14. The apparatus ofclaim 13 comprising a mobile refrigeration or air-conditioningapparatus.
 15. The apparatus of claim 13 comprising a stationaryrefrigeration, air-conditioning or heat pump apparatus.
 16. Theapparatus of claim 13 comprising a chiller.
 17. The apparatus of claim13 comprising a heat pump.